Novel carbazole derivative and chemically amplified radiation-sensitive resin composition

ABSTRACT

A carbazole derivative of the following formula (1),  
                 
 
     wherein R 1  and R 2  individually represent a hydrogen atom or a monovalent organic group, or R 1  and R 2  form, together with the carbon atom to which R 1  and R 2  bond, a divalent organic group having a 3-8 member carbocyclic structure or a 3-8 member heterocyclic structure, and R 3  represents a hydrogen atom or a monovalent organic group. The carbazole derivative is suitable as an additive for increasing sensitivity of a chemically amplified resist. A chemically amplified radiation-sensitive resin composition, useful as a chemically amplified resist, comprising the carbazole derivative is also disclosed.

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] The present invention relates to a novel carbazole derivative anda chemically amplified radiation-sensitive resin composition comprisingthe carbazole derivative suitable as a chemically-amplified resistuseful for microfabrication utilizing various types of radiationrepresented by deep ultraviolet rays such as a KrF excimer laser, ArFexcimer laser, EUV, or F₂ excimer laser, X-rays such as synchrotronradiation, or charged particle rays such as electron beams.

[0003] 2. Description of the Background Art

[0004] In the field of microfabrication represented by fabrication ofintegrated circuit devices, lithographic technology enablingmicrofabrication with a line width of 0.20 μm or less is demanded inrecent years in order to achieve a higher degree of integration.

[0005] A conventional lithographic process utilizes near ultravioletrays such as an i-line radiation. It is known in the art thatmicrofabrication with a line width of a sub-quarter micron order usingnear ultraviolet rays is very difficult.

[0006] Therefore, use of radiation with a shorter wavelength has beenstudied for enabling microfabrication with a line width of 0.20 μm orless. As radiation with a shorter wavelength, deep ultraviolet raysrepresented by a line spectrum of a mercury lamp and an excimer laser,X-rays, electron beams, and the like can be given. Of these, a KrFexcimer laser (wavelength: 248 nm), an ArF excimer laser (wavelength:193nm), and an F₂excimer laser (wavelength: 157 nm) have attractedattention.

[0007] As a resist applicable to the shorter wavelength radiations, anumber of resists utilizing a chemical amplification effect between acomponent having an acid-dissociable functional group and a photoacidgenerator which generates an acid upon irradiation (hereinafter called“exposure”) has been proposed. Such a resist is hereinafter called achemically amplified resist.

[0008] As a chemically amplified resist, Japanese Patent Publication No.27660/1990 discloses a composition comprising a polymer having a t-butylester group of a carboxylic acid or t-butylcarbonate group of phenol anda photoacid generator. This composition utilizes the effect of thepolymer to release a t-butyl ester group or t-butyl carbonate group bythe action of an acid generated upon exposure to form an acidicfunctional group such as a carboxylic group or a phenolic hydroxylgroup, which renders an exposed area on a resist film readily soluble inan alkaline developer.

[0009] In recent years, in addition to high limit resolution and highprocess margin, a high sensitivity to radiations is demanded ofchemically amplified resists as a factor determining productivity of aphotolithographic process.

[0010] Reducing the amount of basic substance which is a component ofchemically amplified resists is one of the methods of increasing thesensitivity of the chemically amplified resists. This method, however,not only involves a decrease in the amount of acids produced by aphotoacid generator, which gives rise to unduly roughened patternsurfaces, but also impairs environmental resistance of the resist suchas poor PED stability, which is an indication of line width stabilityagainst a fluctuated period of time from exposure to post heattreatment. One method for obviating this problem is to increase theamount of photoacid generator. However, an increased amount of photoacidgenerator decreases radiation transmissivity through resist films,resulting in a trapezoid pattern profile rather than a desirablerectangular pattern profile.

[0011] In an effort of increasing sensitivity by the use of additives,Japanese Patent Application Laid-open No.34272/2000 discloses a methodof adding a cyclic 1,2-diolmonosulfonate compound as an agent to assistacid generation. However, this method may affect storage stability ofradiation-sensitive resin compositions. When the photoacid generator isaccidentally decomposed for some reason, an acid may be rapidly produceddue to the action of the acid generation assisting agent.

[0012] The effect of carbazole compounds to increase the sensitivity ofsuccinimide esters used as a photoacid generator has been reported (J.Am. Chem. Soc. 1988, 110,8736). However, this type of compound is highlytoxic and readily sublimable. The compound may splash when formingresist patterns, soils the exposure apparatus, and may have an adverseeffect on human bodies.

[0013] Accordingly, development of a non-sublimable resist additivecapable of increasing sensitivity without affecting basic photo-resistperformance such as high resolution and pattern profile, and providing achemically amplified radiation-sensitive resin composition possessinghigh environmental resistance and storage stability is strongly desired.

[0014] Therefore, an object of the present invention is to provide anovel carbazole derivative which is very useful as a component forincreasing sensitivity of a chemically amplified resist havingsensitivity to radiation such as deep ultraviolet rays represented by aKrF excimer laser, ArF excimer laser, and F₂ excimer laser, and aradiation-sensitive resin composition comprising such a carbazolederivative exhibiting superior sensitivity as a resist without affectingbasic resist performance such as resolution, pattern profile, andstability to resist fluctuations of the period of time from exposure topost heat treatment, and suitably used as a chemically amplified resistpossessing excellent environmental resistance and storage stability.

SUMMARY OF THE INVENTION

[0015] The above object can be solved in the present invention by acarbazole derivative of the following formula (1),

[0016] wherein R¹ and R² individually represent a hydrogen atom or amonovalent organic group, or R¹ and R² form, together with the carbonatom to which R¹ and R² bond, a divalent organic group having a 3-8member carbocyclic structure or a 3-8 member heterocyclic structure, andR³ represents a hydrogen atom or a monovalent organic group.

[0017] The above object can be further solved in the present inventionby a chemically amplified radiation-sensitive resin compositioncomprising the carbazole derivative of the above formula (1).

[0018] Other objects, features and advantages of the invention willhereinafter become more readily apparent from the following description.

BRIEF DESCRIPTION OF THE DRAWINGS

[0019]FIG. 1 is an IR absorption spectrum of the carbazole derivative(1) prepared in Synthetic Example 2.

[0020]FIG. 2 is a ¹H-NMR spectrum of the carbazole derivative (1)prepared in Synthetic Example 2.

[0021]FIG. 3 is a UV absorption spectrum of the carbazole derivative (1)prepared in Synthetic Example 2.

DETAILED DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS

[0022] The present invention will be described in detail below.

Carbazole derivative (1)

[0023] The carbazole derivative of the present invention, represented bythe above formula (1) (hereinafter referred to as “carbazole derivative(1)”), possesses a carbazole skeleton, which is a chromophore orlight-absorbing site in the molecule, and exhibits the effect ofsensitizing photoacid generators such as an onium salt, sulfonimide, anddisulfonyl diazomethane. This compound does not sublimate because of thenon-plane structure due to bonding of the carboxylic ester moiety via acarbon atom with an SP³ orbit.

[0024] As examples of the monovalent organic group represented by R¹andR²in the carbazole derivative (1), linear, branched, or cyclic alkylgroups having 1-12 carbon atoms, aromatic hydrocarbon groups having 6-20carbon atoms, oxygen-containing organic groups, and nitrogen-containingorganic groups can be given.

[0025] As examples of the alkyl groups, a methyl group, ethyl group,n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group,1-methylpropyl group, t-butyl group, cyclopentyl group, and cyclohexylgroup can be given. As examples of the aromatic hydrocarbon groups, aphenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylylgroup, 2, 6-xylyl group, 3,5-xylyl group, mesityl group, o-cumenylgroup, m-cumenyl group, p-cumenyl group, benzyl group, phenethyl group,1-naphthyl group, and 2-naphthyl group can be given.

[0026] The following groups can be given as examples of theoxygen-containing organic groups: a carboxyl group; linear, branched, orcyclic hydroxyalkyl groups having 1-8 carbon atoms such as a1-hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group,1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group,1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group,4-hydroxybutyl group, 3-hydroxycyclopentyl group, and4-hydroxycyclohexyl group; linear, branched, or cyclic alkoxyl groupshaving 1-8 carbon atoms such as a methoxy group, ethoxy group, n-propoxygroup, i-propoxygroup, n-butoxygroup, 2-methylpropoxy group,1-methylpropoxy group, t-butoxygroup, cyclopentyloxy group, andcyclohexyloxy group; linear, branched, or cyclic alkoxyalkyl groupshaving 2-10 carbon atoms such as a methoxymethyl group, ethoxymethylgroup, n-propoxymethyl group, i-propoxymethyl group, n-butoxymethylgroup, t-butoxymethyl group, cyclopentyloxymethyl group, andcyclohexyloxymethyl group; linear or branched 1-alkoxyalkoxy groupshaving 2-10 carbon atoms such as a 1-methoxyethoxy group, 1-ethoxyethoxygroup, 1-n-propoxyethoxy group, 1-n-butoxyethoxy group,1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group,1-methoxypropoxy group, 1-ethoxypropoxy group, 1-cyclopentyloxyethoxygroup, and 1-cyclohexyloxyethoxy group; linear, branched, or cyclicalkoxycarbonyloxy groups having 2-9 carbon atoms such as amethoxycarbonyloxy group, ethoxycarbonyl oxy group, n-propoxycarbonyloxygroup, i-propoxycarbonyloxy group, n-butoxycarbonyloxy group,t-butoxycarbonyloxy group, cyclopentyloxycarbonyloxy group,andcyclohexyloxycarbonyloxy group; linear or branched(1-alkoxyalkoxy)alkyl groups having 3-11 carbon atoms such as a(1-methoxyethoxy)methyl group, (1-ethoxyethoxy)methyl group,(1-n-propoxyethoxy)methyl group, (1-n-butoxyethoxy)methyl group,(1-cyclopentyloxyethoxy)methyl group, (1-cyclohexyloxyethoxy)methylgroup, (1-methoxypropoxy)methyl group, and (1-ethoxypropoxy)methylgroup; linear, branched, or cyclic alkoxycarbonyloxyalkyl groups having3-10 carbon atoms such as a methoxycarbonyloxymethyl group,ethoxycarbonyloxymethyl group, n-propoxycarbonyloxymethyl group,i-propoxycarbonyloxymethyl group, n-butoxycarbonyloxymethyl group,t-butoxycarbonyloxymethyl group, cyclopentyloxycarbonyloxymethyl group,and cyclohexyloxycarbonyloxymethyl group; a tetrahydrofuranyloxy group,tetrahydropyranyloxy group, tetrahydrofuranyloxymethyl group,tetrahydropyranyloxymethyl group, and the like.

[0027] Examples of the nitrogen-containing organic groups include acyano group; linear, branched, or cyclic cyanoalkyl groups having 2-9carbon atoms such as a cyanomethyl group, 1-cyanoethyl group,2-cyanoethyl group, 1-cyanopropyl group, 2-cyanopropyl group,3-cyanopropyl group, 1-cyanobutyl group, 2-cyanobutyl group,3-cyanobutyl group, 4-cyanobutyl group, 3-cyanocyclopentyl group, and4-cyanocyclohexyl group; and the like.

[0028] As examples of the divalent organic group having a 3-8 membercarbocyclic structure formed by R¹, R², and the carbon atom to which thegroups R¹ and R² bond, groups derived from a cyclopropane, cyclobutane,cyclopentane, cyclohexane, cyclohexene, or cyclooctane can be given.

[0029] As examples of the divalent organic group having a 3-8 membercarbocyclic structure formed by R¹, R², and the carbon atom to which thegroups R¹ and R² bond, groups derived from a tetrahydrofuran,tetrahydropyran, 1,4-dioxane, tetrahydrothiofuran, andtetrahydrothiopyran can be given.

[0030] As the groups R¹ and R² in the carbazole derivative, a hydrogenatom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butylgroup, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, phenylgroup, and benzyl group are preferable. As the divalent organic grouphaving an alicyclic ring formed by R¹, R², and the carbon atom to whichR¹ and R² bond, groups derived from a cyclohexane or the like arepreferable.

[0031] As examples of the monovalent organic group represented by R³,linear, branched, or cyclic alkyl groups having 1-12 carbon atoms,aromatic hydrocarbon groups having 6-20 carbon atoms, oxygen-containingorganic groups, nitrogen-containing organic groups, and acid-dissociableorganic groups can be given.

[0032] As examples of the linear, branched, or cyclic alkyl groupshaving 1-12 carbon atoms, aromatic hydrocarbon groups having 6-20 carbonatoms, oxygen-containing organic groups, and nitrogen-containing organicgroups represented by R³, the corresponding groups given as examples ofR¹ and R²can be given. Of these groups, i-propyl group, 1-methylpropylgroup, t-butyl group, cyclic alkyl group, benzyl group, cyclichydroxyalkyl group, alkoxymethyl group, (1-alkoxyalkoxy)methyl group,alkoxycarbonyloxymethyl group, tetrahydrofuranyloxymethyl group,tetrahydropyranyloxymethyl group, and cyclic cyanoalkyl group areincluded in the acid-dissociable organic groups.

[0033] As examples of other acid-dissociable organic groups representedby R³, a substituted methyl group, 1-substituted ethyl group, 1-branchedalkyl group, silyl group, germyl group, alkoxycarbonyl group, acylgroup, and cyclic acid-dissociable group can be given.

[0034] As examples of the above substituted methyl group, amethylthiomethyl group, ethylthiomethyl group, benzyloxymethyl group,benzylthiomethyl group, phenacyl group, bromophenacyl group,methoxyphenacyl group, methylthiophenacyl group, a-methylphenacyl group,cyclopropylmethyl group, diphenylmethyl group, triphenylmethyl group,bromobenzyl group, nitrobenzyl group, methoxybenzyl group,methylthiobenzyl group, ethoxybenzyl group, ethylthiobenzyl group, andpiperonyl group can be given.

[0035] As examples of the 1-substituted methyl groups, a 1-methoxyethylgroup, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethylgroup, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-ethoxypropylgroup, 1-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenoxyethylgroup, 1-phenylthioethyl group, 1,1-diphenoxyethyl group,1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethylgroup, 1-phenylethyl group, 1,1-diphenylethyl group,1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group,1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethyl group,1-n-butoxycarbonylethyl group, and 1-t-butoxycarbonylethyl group can begiven.

[0036] As examples of the 1-branched alkyl groups, a 1,1-dimethylpropylgroup, 1-methylbutyl group, and 1,1-dimethylbutyl group can be given.

[0037] As examples of the silyl groups, tricarbylsilyl groups such as atrimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilylgroup, triethylsilyl group, i-propyldimethylsilyl group,methyldi-i-propylsilyl group, tri-i-propylsilyl group,t-butyldimethylsilyl group, methyldi-t-butylsilyl group,tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilylgroup, and triphenylsilyl group can be given.

[0038] As examples of the germyl groups, tricarbylgermyl groups such asa trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermylgroup, triethylgermyl group, i-propyldimethylgermyl group,methyldi-i-propylgermyl group, tri-i-propylgermyl group,t-butyldimethylgermyl group, methyldi-t-butylgermyl group,tri-t-butylgermyl group, phenyldimethylgermyl group,methyldiphenylgermyl group, and triphenylgermyl group can be given.

[0039] As examples ofthealkoxycarbonyl group, amethoxycarbonyl group,ethoxycarbonyl group, i-propoxycarbonyl group, and t-butoxycarbonylgroup can be given.

[0040] As examples of the acyl groups, an acetyl group, propionyl group,butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloylgroup, isovaleryl group, lauroyl group, myristoyl group, palmitoylgroup, stearoyl group, oxalyl group, malonyl group, succinyl group,glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoylgroup, sebacoyl group, acryloyl group, propioloyl group, methacryloylgroup, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group,mesaconoyl group, campholoyl group, benzoyl group, phthaloyl group,isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group,hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group,thenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonylgroup, and mesyl group can be given.

[0041] As examples of the cyclic acid-dissociable group, a cyclopropylgroup, 3-methylcyclopentyl group, 4-methylcyclohexyl group, cyclohexenylgroup, 4-methoxycyclohexyl group, tetrahydrofuranyl group,tetrahydropyranyl group, tetrahydrothiofuranyl group,tetrahydrothiopyranyl group, 3-bromotetrahydropyranyl group,4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group,and 3-tetrahydrothiophene-1,1-dioxide can be given.

[0042] As the acid-dissociable organic groups represented by R³, ani-propyl group, 1-methylpropyl group, t-butyl group, cyclohexyl group,benzyl group, t-butoxycarbonylmethyl group, 1-methoxyethyl group,1-ethoxyethyl group, trimethylsilyl group, t-butoxycarbonyl group,tetrahydrofuranyl group, tetrahydropyranyl group, tetrahydrothiofuranylgroup, tetrahydrothiopyranyl group, and the like are preferable.

[0043] As the group R³in the carbazole derivative (1), a hydrogen atom,methyl group, ethyl group, n-propyl group, n-butyl group, 2-methylpropylgroup, and phenyl group, as well as the acid-dissociable organic groupssuch as an i-propyl group, 1-methylpropyl group, t-butyl group,cyclohexyl group, benzyl group, t-butoxycarbonylmethyl group,1-methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group,t-butoxycarbonyl group, tetrahydrofuranyl group, tetrahydropyranylgroup, tetrahydrothiofuranyl group, tetrahydrothiopyranyl group, and thelike are preferable. Of these groups, i-propyl group, t-butyl group,cyclohexyl group, benzyl group, and the like are particularlypreferable.

[0044] Specific preferable examples of the carbazole derivative (1)include the compounds of the following formulas (1-1) to (1-78).

[0045] The carbazole derivative (1) can be synthesized by reactingcarbazole and an α-bromocarboxylic acid such as bromoacetic acid or anα-bromocarboxylic acid ester such as t-butyl bromoacetate in thepresence of a basic catalyst in an appropriate solvent.

[0046] As the basic catalyst, a super-strong basic catalyst such assodium amide, sodium hydride, n-butyl lithium, and1,8-diazabicyclo[5.4.0]undec-7-ene; strong basic catalyst such asmethoxy potassium, ethoxy potassium, and t-butoxy potassium; weak basiccatalyst such as triethylamine and tri-n-butyl amine; and the like canbe given.

[0047] Of these basic catalysts, super-strong basic catalysts and strongbasic catalysts are preferable. These basic catalysts may be used eitherindividually or in combination of two or more.

[0048] As examples of the solvents, dimethylformamide,dimethylacetamide, dimethylsulfoxide, t-butanol, acetone, acetonitrile,tetrahydrofuran, chloroform, and methylene chloride can be given.

[0049] These solvents may be used either individually or in combinationof two or more.

[0050] The reaction for synthesizing the carbazole derivative (1) iscarried out at a temperature of usually −20° C. to 150° C., andpreferably 0 to 70° C., for usually 1 minute to 96 hours, and preferably30 minutes to 48 hours.

[0051] The carbazole derivative (1) is not only suitable particularly asan additive for increasing sensitivity of chemically amplifiedradiation-sensitive resin compositions used as a chemically amplifiedresist, but also can be used as an intermediate for synthesizing othercarbazole derivatives having a carbazole ring structure.

[0052] Chemically amplified radiation-sensitive resin composition

[0053] The other components for the chemically amplifiedradiation-sensitive resin composition of the present invention are notspecifically limited in as much as the composition contains thecarbazole derivative (1) as an essential component and can function as achemically-amplified resist. The following chemically amplifiedradiation-sensitive resin composition can be given as a preferableexample of such a composition.

[0054] A chemically amplified radiation sensitive resin compositioncomprising (A) the carbazole derivative (1), (B) an acid-dissociablegroup-containing resin which is insoluble or scarcely soluble in alkali,but becomes alkali soluble when the acid-dissociable group dissociates(hereinafter referred to as “acid-dissociable group-containing resin(B)”), and (C) a photoacid generator (hereinafter referred to as “acidgenerator (C)”) can be given as a preferable example (this resincomposition is hereinafter referred to as “chemically amplifiedradiation sensitive resin composition [I]”).

[0055] The chemically amplified radiation sensitive resin composition[I] will now be described.

[0056] Carbazole derivative (1)

[0057] As the carbazole derivative (1) used as component (A) in theradiation-sensitive resin composition [I], compounds shown by theformulas (1-1), (1-6), (1-7), (1-8), (1-10), (1-20), (1-34), and (1-73)are particularly preferable.

[0058] The carbazole derivatives (I) can be used either individually orin combination of two or more in the chemically amplified radiationsensitive resin composition [I].

[0059] The amount of the carbazole derivatives (1) used in thechemically amplified radiation sensitive resin composition [I] ispreferably 0.1-40 parts by weight, more preferably 0.2-20 parts byweight, and particularly preferably 1-10parts by weight for 100 parts byweight of the acid-dissociable group-containing resin (B).

[0060] Acid-dissociable group-containing resin (B)

[0061] As the acid-dissociable group-containing resin (B), a resin,insoluble or scarcely soluble in alkali by itself, obtainable from analkali-soluble resin containing one or more acid functional groups suchas a phenolic hydroxyl group or carboxyl group by replacing one or morehydrogen atoms in the acid functional groups with acid-dissociablegroups can be given.

[0062] If 50% or more of the initial film thickness of a resist filmremains after development when a resist film made only from theacid-dissociable group-containing resin (B) is developed under the samealkaline development conditions employed for forming a resist patternusing a resist film formed from a radiation-sensitive resin compositioncomprising the acid-dissociable group-containing resin (B), such acharacteristic of the acid-dissociable group-containing resin (B) isreferred to as “insoluble or scarcely soluble in alkali” in the presentinvention.

[0063] As examples of such an acid-dissociable group in theacid-dissociable group-containing resin (B), a substituted methyl group,1-substituted ethyl group, 1-branched alkyl group, silyl group, germylgroup, alkoxycarbonyl group, acyl group, cyclic acid-dissociable group,and the like can be given.

[0064] As examples of the substituted methyl group, a methoxymethylgroup, methylthiomethyl group, ethoxymethyl group, ethylthiomethylgroup, methoxyethoxymethyl group, benzyloxymethyl group,benzylthiomethyl group, phenacyl group, bromophenacyl group,methoxyphenacyl group, methylthiophenacyl group, α-methylphenacyl group,cyclopropylmethyl group, benzyl group, diphenylmethyl group,triphenylmethyl group, bromobenzyl group, nitrobenzyl group,methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group,ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group,ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group,i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, andt-butoxycarbonylmethyl group can be given.

[0065] As examples of the 1-substituted methyl group, a 1-methoxyethylgroup, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethylgroup, 1-ethylthioethyl group, 1,1-diethoxyethyl group, 1-ethoxypropylgroup, 1-propoxyethyl group, 1-cyclohexyloxyethyl group, 1-phenoxyethylgroup, 1-phenylthioethyl group, 1,1-diphenoxyethyl group,1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethylgroup, 1-phenylethyl group, 1,1-diphenylethyl group,1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group,1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethyl group,1-n-butoxycarbonylethyl group, and 1-t-butoxycarbonylethyl group can begiven.

[0066] As examples of the 1-branched alkyl group, an i-propyl group,sec-butyl group, t-butyl group, 1, 1-dimethylpropyl group, 1-methylbutylgroup, and 1,1-dimethylbutyl group can be given.

[0067] As examples of the silyl groups, tricarbylsilyl groups such as atrimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilylgroup, triethylsilyl group, i-propyldimethylsilyl group,methyldi-i-propylsilyl group, tri-i-propylsilyl group,t-butyldimethylsilyl group, methyldi-t-butylsilyl group,tri-t-butylsilyl group, phenyldimethylsilyl group, methyldiphenylsilylgroup, and triphenylsilyl group can be given.

[0068] As examples of the germyl group, tricarbylgermyl groups such as atrimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermylgroup, triethylgermyl group, i-propyldimethylgermyl group,methyldi-i-propylgermyl group, tri-i-propylgermyl group,t-butyldimethylgermyl group, methyldi-t-butylgermyl group,tri-t-butylgermyl group, phenyldimethylgermyl group,methyldiphenylgermyl group, and triphenylgermyl group can be given.

[0069] As examples of the alkoxycarbonyl group, amethoxycarbonyl group,ethoxycarbonyl group, i-propoxycarbonyl group, and t-butoxycarbonylgroup can be given.

[0070] As examples of the acyl group, an acetyl group, propionyl group,butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloylgroup, isovaleryl group, lauroyl group, myristoyl group, palmitoylgroup, stearoyl group, oxalyl group, malonyl group, succinyl group,glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoylgroup, sebacoyl group, acryloyl group, propioloyl group, methacryloylgroup, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group,mesaconoyl group, campholoyl group, benzoyl group, phthaloyl group,isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group,hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group,thenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonylgroup, and mesyl group can be given.

[0071] As examples of the cyclic acid-dissociable group, a cyclopropylgroup, cyclopentyl group, cyclohexyl group, cyclohexenyl group,4-methoxycyclohexyl group, tetrahydropyranyl group, tetrahydrofuranylgroup, tetrahydrothiofuranyl group, tetrahydrothiopyranyl group,3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group,4-methoxytetrahydrothiopyranyl group, and3-tetrahydrothiophene-1,1-dioxide group can be given.

[0072] Of these acid-dissociable groups, a t-butyl group, benzyl group,1-methoxyethyl group, 1-ethoxyethyl group, trimethylsilyl group,t-butoxycarbonyl group, t-butoxycarbonylmethyl group, tetrahydrofuranylgroup, tetrahydropyranyl group, tetrahydrothiofuranyl group,tetrahydrothiopyranyl group, and the like are preferable.

[0073] As particularly preferable acid-dissociable group-containingresin (B) of the present invention, a resin obtainable from apoly(p-hydroxystyrene), a copolymer of p-hydroxystyrene andp-hydroxy-α-methylstyrene, a copolymer of p-hydroxy styrene and styrene,or a copolymer of p-hydroxy styrene and/or p-hydroxy-α-methylstyrene,and (meth) acrylic acid by replacing a part or all of the hydrogen atomsin the phenolic hydroxyl groups or the hydrogen atoms in the carboxylicgroups with the above-mentioned acid-dissociable groups, particularlywith a group selected from the group consisting of a t-butyl group,benzyl group, 1-methoxyethyl group, 1-ethoxyethyl group, trimethylsilylgroup, t-butoxycarbonyl group, t-butoxycarbonylmethyl group,tetrahydropyranyl group, tetrahydrofuranyl group, tetrahydrothiopyranylgroup, and tetrahydrothiofuranyl group can be given.

[0074] The amount of the acid-dissociable groups introduced into theacid-dissociable group-containing resin (B) (the amount of the number ofthe acid-dissociable groups in the total number of non-protected acidfunctional groups and acid-dissociable groups in the acid-dissociablegroup-containing resin (B)) is preferably 10-100%, and still morepreferably 15-100%, although the amount varies depending on the types ofacid-dissociable groups and the alkali-soluble resin into which theacid-dissociable groups are introduced.

[0075] The polystyrene-reduced weight average molecular weight(hereinafter referred to as “Mw”) of the acid-dissociablegroup-containing resin (B) determined by gel permeation chromatography(GPC) is preferably 1,000-150,000, and more preferably 3,000-100,000.

[0076] The ratio of Mw to the polystyrene-reduced number averagemolecular weight (hereinafter referred to as “Mn”) determined by gelpermeation chromatography (Mw/Mn) of the acid-dissociablegroup-containing resin (B) is usually 1-10, and preferably 1-5.

[0077] The acid-dissociable group-containing resin (B) can be prepared,for example, by introducing one or more acid-dissociable groups into analkali-soluble resin, by (co)polymerization of monomers containing oneor more acid-dissociable groups, or by (co)polycondensation ofpolycondensable components containing one or more acid-dissociablegroups.

[0078] The acid-dissociable group-containing resin (B) can be usedeither individually or in combination of two or more, or in combinationwith one or more alkali-soluble resins such as a poly(p-hydroxystyrene)or a novolak resin in the chemically amplified radiation sensitive resincomposition [I].

[0079] Acid generator (C)

[0080] The photoacid generator (C) of the present invention is acomponent which generates an acid upon exposure.

[0081] As such an acid generator (C), (1) onium salt compounds, (2)sulfone compounds, (3) sulfonate compounds, (4) sulfonimide compounds,(5) disulfonyldiazomethane compounds, (6) disulfonylmethane compounds,(7) oxime sulfonate compounds, (8) hydrazine sulfonate compounds, andthe like can be given.

[0082] Examples of these acid generators (C) are as follows:

[0083] (1) Onium salt compounds

[0084] As examples of onium salt compounds, iodonium salts, sulfoniumsalts (including thiophenium salts), phosphonium salts, diazonium salts,ammonium salts, and pyridinium salts can be given.

[0085] Specific examples of onium salts include:

[0086] bis(4-t-butylphenyl) iodonium trifluoromethanesulfonate,

[0087] bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate,

[0088] bis(4-t-butylphenyl)iodonium perfluoro-n-octanesulfonate,

[0089] bis(4-t-butylphenyl)iodonium pyrenesulfonate,

[0090] bis(4-t-butylphenyl)iodonium n-dodecylbenzenesulfonate,

[0091] bis(4-t-butylphenyl)iodonium p-toluenesulfonate,

[0092] bis(4-t-butylphenyl)iodonium benzenesulfonate,

[0093] bis(4-t-butylphenyl)iodonium 10-camphorsulfonate,

[0094] bis(4-t-butylphenyl)iodonium n-octanesulfonate,

[0095] bis(4-t-butylphenyl)iodonium

[0096] 2-trifluoromethylbenzenesulfonate,

[0097] bis(4-t-butylphenyl)iodonium

[0098] 4-trifluoromethylbenzenesulfonate,

[0099] bis(4-t-butylphenyl)iodonium perfluorobenzenesulfonate,

[0100] diphenyliodonium trifluoromethanesulfonate,

[0101] diphenyliodonium nonafluoro-n-butanesulfonate,

[0102] diphenyliodonium perfluoro-n-octanesulfonate,

[0103] diphenyliodonium pyrenesulfonate,

[0104] diphenyliodonium n-dodecylbenzenesulfonate,

[0105] diphenyliodonium p-toluenesulfonate,

[0106] diphenyliodonium benzenesulfonate,

[0107] diphenyliodonium 10-camphorsulfonate,

[0108] diphenyliodonium n-octanesulfonate,

[0109] diphenyliodonium 2-trifluoromethylbenzenesulfonate,

[0110] diphenyliodonium 4-trifluoromethylbenzenesulfonate,

[0111] diphenyliodonium perfluorobenzenesulfonate,

[0112] di(p-tolyl)iodonium trifiuoromethanesulfonate,

[0113] di(p-tolyl)iodonium nonafluoro-n-butanesulfonate,

[0114] di(p-tolyl)iodonium perfluoro-n-octanesulfonate,

[0115] di(p-tolyl)iodonium pyrenesulfonate,

[0116] di(p-tolyl)iodonium n-dodecylbenzenesulfonate,

[0117] di(p-tolyl)iodonium p-toluenesulfonate,

[0118] di(p-tolyl)iodonium benzenesulfonate,

[0119] di(p-tolyl)iodonium 10-camphorsulfonate,

[0120] di(p-tolyl)iodonium n-octanesulfonate,

[0121] di(p-tolyl)iodonium 2-trifluoromethylbenzenesulfonate,

[0122] di(p-tolyl)iodonium 4-trifluoromethylbenzenesulfonate,

[0123] di(p-tolyl)iodonium perfluorobenzenesulfonate,

[0124] di(3,4-dimethylphenyl)iodonium trifluoromethanesulfonate,

[0125] di(3,4dimethylphenyl)iodonium

[0126] nonafluoro-n-butanesulfonate,

[0127] di(3,4-dimethylphenyl)iodonium perfluoro-n-octanesulfonate,

[0128] di(3,4-dimethylphenyl)iodonium pyrenesulfonate,

[0129] di(3,4-dimethylphenyl)iodonium n-dodecylbenzenesulfonate,

[0130] di(3,4-dimethylphenyl)iodonium p-toluenesulfonate,

[0131] di(3,4-dimethylphenyl)iodonium benzenesulfonate,

[0132] di(3,4-dimethylphenyl)iodonium 10-camphorsulfonate,

[0133] di(3,4-dimethylphenyl)iodonium n-octanesulfonate,

[0134] di(3,4-dimethylphenyl)iodonium

[0135] 2-trifluoromethylbenzenesulfonate,

[0136] di(3,4-dimethylphenyl)iodonium

[0137] 4-trifluoromethylbenzenesulfonate,

[0138] di(3,4-dimethylphenyl)iodonium perfluorobenzenesulfonate,

[0139] p-nitrophenyl.phenyliodonium trifluoromethanesulfonate,

[0140] p-nitrophenyl.phenyliodonium nonafluoro-n-butanesulfonate,

[0141] p-nitrophenyl.phenyliodonium perfluoro-n-octanesulfonate,

[0142] p-nitrophenyl.phenyliodonium pyrenesulfonate,

[0143] p-nitrophenyl.phenyliodonium n-dodecylbenzenesulfonate,

[0144] p-nitrophenyl.phenyliodonium p-toluenesulfonate,

[0145] p-nitrophenyl.phenyliodonium benzenesulfonate,

[0146] p-nitrophenyl.phenyliodonium 10-camphorsulfonate,

[0147] p-nitrophenyl.phenyliodonium n-octanesulfonate,

[0148] p-nitrophenyl.phenyliodonium

[0149] 2trifluoromethylbenzenesulfonate,

[0150] p-nitrophenyl.phenyliodonium

[0151] 4-trifluoromethylbenzenesulfonate,

[0152] p-nitrophenyl.phenyliodonium perfluorobenzenesulfonate,

[0153] di(m-nitrophenyl)iodonium trifluoromethanesulfonate,

[0154] di(m-nitrophenyl)iodonium nonafluoro-n-butanesulfonate,

[0155] di(m-nitrophenyl)iodonium perfluoro-n-octanesulfonate,

[0156] di(m-nitrophenyl)iodonium pyrenesulfonate,

[0157] di(m-nitrophenyl)iodonium n-dodecylbenzenesulfonate,

[0158] di(m-nitrophenyl)iodonium p-toluenesulfonate,

[0159] di(m-nitrophenyl)iodonium benzenesulfonate,

[0160] di(m-nitrophenyl)iodonium 10-camphorsulfonate,

[0161] di(m-nitrophenyl)iodonium n-octanesulfonate,

[0162] di(m-nitrophenyl)iodonium

[0163] 2-trifluoromethylbenzenesulfonate,

[0164] di(m-nitrophenyl)iodonium

[0165] 4-trifluoromethylbenzenesulfonate,

[0166] di(m-nitrophenyl)iodonium perfluorobenzenesulfonate,

[0167] p-methoxyphenyl.phenyl iodonium trifluoromethanesulfonate,

[0168] p-methoxyphenyl.phenyliodonium

[0169] nonafluoro-n-butanesulfonate,

[0170] p-methoxyphenyl.phenyliodonium perfluoro-n-octanesulfonate,

[0171] p-methoxyphenyl.phenyliodonium pyrenesulfonate,

[0172] p-methoxyphenyl.phenyliodonium n-dodecylbenzenesulfonate,

[0173] p-methoxyphenyl.phenyliodonium p-toluenesulfonate,

[0174] p-methoxyphenyl.phenyliodonium benzenesulfonate,

[0175] p-methoxyphenyl.phenyliodonium 10-camphorsulfonate,

[0176] p-methoxyphenyl.phenyliodonium n-octanesulfonate,

[0177] p-methoxyphenyl.phenyliodonium

[0178] 2-trifluoromethylbenzenesulfonate,

[0179] p-methoxyphenyl.phenyliodonium

[0180] 4-trifluoromethylbenzenesulfonate,

[0181] p-methoxyphenyl.phenyliodonium perfluorobenzenesulfonate,

[0182] di(p-chlorophenyl)iodoniumtrifluoromethane sulfonate,

[0183] di(p-chlorophenyl)iodonium nonafluoro-n-butanesulfonate,

[0184] di(p-chlorophenyl)iodonium perfluoro-n-octanesulfonate,

[0185] di(p-chlorophenyl)iodonium pyrenesulfonate,

[0186] di(p-chlorophenyl)iodonium n-dodecylbenzenesulfonate,

[0187] di(p-chlorophenyl)iodonium p-toluenesulfonate,

[0188] di(p-chlorophenyl)iodonium benzenesulfonate,

[0189] di(p-chlorophenyl)iodonium 10-camphorsulfonate,

[0190] di(p-chlorophenyl)iodonium n-octanesulfonate,

[0191] di(p-chlorophenyl)iodonium

[0192] 2-trifluoromethylbenzenesulfonate,

[0193] di(p-chlorophenyl)iodonium

[0194] 4-trifluoromethylbenzenesulfonate,

[0195] di(p-chlorophenyl)iodonium perfluorobenzenesulfonate,

[0196] di(p-trifluoromethylphenyl)iodonium

[0197] trifluoromethanesulfonate,

[0198] di(p-trifluoromethylphenyl)iodonium

[0199] nonafluoro-n-butanesulfonate,

[0200] di(p-trifluoromethylphenyl)iodonium

[0201] perfluoro-n-octanesulfonate,

[0202] di(p-trifluoromethylphenyl)iodonium pyrenesulfonate,

[0203] di(p-trifluoromethylphenyl)iodonium

[0204] n-dodecylbenzenesulfonate,

[0205] di(p-trifluoromethylphenyl)iodonium p-toluenesulfonate,

[0206] di(p-trifluoromethylphenyl)iodonium benzenesulfonate,

[0207] di(p-trifluoromethylphenyl)iodonium 10-camphorsulfonate,

[0208] di(p-trifluoromethylphenyl)iodonium n-octanesulfonate,

[0209] di(p-trifluoromethylphenyl)iodonium

[0210] 2-trifluoromethylbenzenesulfonate,

[0211] di(p-trifluoromethylphenyl)iodonium

[0212] 4-trifluoromethylbenzenesulfonate,

[0213] di(p-trifluoromethylphenyl)iodonium

[0214] perfluorobenzenesulfonate,

[0215] dinaphthyliodonium trifluoromethanesulfonate,

[0216] dinaphthyliodonium nonafluoro-n-butanesulfonate,

[0217] dinaphthyliodonium perfluoro-n-octanesulfonate,

[0218] dinaphthyliodonium pyrenesulfonate,

[0219] dinaphthyliodonium n-dodecylbenzenesulfonate,

[0220] dinaphthyliodonium p-toluenesulfonate,

[0221] dinaphthyliodonium benzenesulfonate,

[0222] dinaphthyliodonium 10-camphorsulfonate,

[0223] dinaphthyliodonium n-octanesulfonate,

[0224] dinaphthyliodonium 2-trifluoromethylbenzenesulfonate,

[0225] dinaphthyliodonium 4-trifluoromethylbenzenesulfonate,

[0226] dinaphthyliodonium perfluorobenzenesulfonate,

[0227] biphenyleneiodonium trifluoromethanesulfonate,

[0228] biphenyleneiodonium nonafluoro-n-butanesulfonate,

[0229] biphenyleneiodonium perfluoro-n-octanesulfonate,

[0230] biphenyleneiodonium pyrenesulfonate,

[0231] biphenyleneiodonium n-dodecylbenzenesulfonate,

[0232] biphenyleneiodonium p-toluenesulfonate,

[0233] biphenyleneiodonium benzenesulfonate,

[0234] biphenyleneiodonium 10-camphorsulfonate,

[0235] biphenyleneiodonium n-octanesulfonate,

[0236] biphenyleneiodonium 2-trifluoromethylbenzenesulfonate,

[0237] biphenyleneiodonium 4-trifluoromethylbenzenesulfonate,

[0238] biphenyleneiodonium perfluorobenzenesulfonate,

[0239] 2-chlorobiphenyleneiodonium trifluoromethanesulfonate,

[0240] 2-chlorobiphenyleneiodonium nonafluoro-n-butanesulfonate,

[0241] 2-chlorobiphenyleneiodonium perfluoro-n-octanesulfonate,

[0242] 2-chlorobiphenyleneiodonium pyrenesulfonate,

[0243] 2-chlorobiphenyleneiodonium n-dodecylbenzenesulfonate,

[0244] 2-chlorobiphenyleneiodonium p-toluenesulfonate,

[0245] 2-chlorobiphenyleneiodonium benzenesulfonate,

[0246] 2-chlorobiphenyleneiodonium 10-camphorsulfonate,

[0247] 2-chlorobiphenyleneiodonium n-octanesulfonate,

[0248] 2-chlorobiphenyleneiodonium

[0249] 2-trifluoromethylbenzenesulfonate,

[0250] 2-chlorobiphenyleneiodonium

[0251] 4-trifluoromethylbenzenesulfonate,

[0252] 2-chlorobiphenyleneiodonium perfluorobenzenesulfonate,

[0253] triphenylsulfonium trifluoromethanesulfonate,

[0254] triphenylsulfonium nonafluoro-n-butanesulfonate,

[0255] triphenylsulfonium perfluoro-n-octanesulfonate,

[0256] triphenylsulfonium pyrenesulfonate,

[0257] triphenylsulfonium n-dodecylbenzenesulfonate,

[0258] triphenylsulfonium p-toluenesulfonate,

[0259] triphenylsulfonium benzenesulfonate,

[0260] triphenylsulfonium 10-camphorsulfonate,

[0261] triphenylsulfonium n-octanesulfonate,

[0262] triphenylsulfonium 2-trifluoromethylbenzenesulfonate,

[0263] triphenylsulfonium 4-trifluoromethylbenzenesulfonate,

[0264] triphenylsulfonium hexafluoroantimonate,

[0265] triphenylsulfonium naphthalenesulfonate,

[0266] triphenylsulfonium perfluorobenzenesulfonate,

[0267] 4-t-butylphenyl.diphenylsulfonium

[0268] trifluoromethanesulfonate,

[0269] 4-t-butylphenyl.diphenylsulfonium

[0270] nonafluoro-n-butanesulfonate,

[0271] 4-t-butylphenyl.diphenylsulfonium

[0272] perfluoro-n-octanesulfonate,

[0273] 4-t-butylphenyl.diphenylsulfonium pyrenesulfonate,

[0274] 4-t-butylphenyl.diphenylsulfonium

[0275] n-dodecylbenzenesulfonate,

[0276] 4-t-butylphenyl.diphenylsulfonium p-toluenesulfonate,

[0277] 4-t-butylphenyl.diphenylsulfonium benzenesulfonate,

[0278] 4-t-butylphenyl.diphenylsulfonium 10-camphorsulfonate,

[0279] 4-t-butylphenyl.diphenylsulfonium n-octanesulfonate,

[0280] 4-t-butylphenyl.diphenylsulfonium

[0281] 2-trifluoromethylbenzenesulfonate,

[0282] 4-t-butylphenyl.diphenylsulfonium

[0283] 4-trifluoromethanebenzenesulfonate,

[0284] 4-t-butylphenyl.diphenylsulfonium

[0285] perfluorobenzenesulfonate,

[0286] 4-t-butoxyphenyl.diphenylsulfonium

[0287] trifluoromethanesulfonate,

[0288] 4-t-butoxyphenyl.diphenylsulfonium

[0289] nonafluoro-n-butanesulfonate,

[0290] 4-t-butoxyphenyl.diphenylsulfonium

[0291] perfluoro-n-octanesulfonate,

[0292] 4-t-butoxyphenyl.diphenylsulfonium pyrenesulfonate,

[0293] 4-t-butoxyphenyl.diphenylsulfonium

[0294] n-dodecylbenzenesulfonate,

[0295] 4-t-butoxyphenyl.diphenylsulfonium p-toluenesulfonate,

[0296] 4-t-butoxyphenyl.diphenylsulfonium benzenesulfonate,

[0297] 4-t-butoxyphenyl.diphenylsulfonium 10-camphorsulfonate,

[0298] 4-t-butoxyphenyl.diphenylsulfonium n-octanesulfonate,

[0299] 4-t-butoxyphenyl.diphenylsulfonium

[0300] 2-trifluoromethylbenzenesulfonate,

[0301] 4-t-butoxyphenyl.diphenylsulfonium

[0302] 4-trifluoromethylbenzenesulfonate,

[0303] 4-t-butoxyphenyl.diphenylsulfonium

[0304] perfluorobenzenesulfonate,

[0305] 4-hydroxyphenyl.diphenylsulfonium

[0306] trifluoromethanesulfonate,

[0307] 4-hydroxyphenyl.diphenylsulfonium

[0308] nonafluoro-n-butanesulfonate,

[0309] 4-hydroxyphenyl.diphenylsulfonium

[0310] perfluoro-n-octanesulfonate,

[0311] 4-hydroxyphenyl.diphenylsulfonium pyrenesulfonate,

[0312] 4-hydroxyphenyl.diphenylsulfonium

[0313] n-dodecylbenzenesulfonate,

[0314] 4-hydroxyphenyl.diphenylsulfonium p-toluenesulfonate,

[0315] 4-hydroxyphenyl.diphenylsulfonium benzenesulfonate,

[0316] 4-hydroxyphenyl.diphenylsulfonium 10-camphorsulfonate,

[0317] 4-hydroxyphenyl.diphenylsulfonium n-octanesulfonate,

[0318] 4-hydroxyphenyl.diphenylsulfonium

[0319] 2-trifluoromethylbenzenesulfonate,

[0320] 4-hydroxyphenyl.diphenylsulfonium

[0321] 4-trifluoromethylbenzenesulfonate,

[0322] 4-hydroxyphenyl.diphenylsulfonium

[0323] perfluorobenzenesulfonate,

[0324] tri(p-methoxyphenyl)sulfonium trifluoromethanesulfonate,

[0325] tri(p-methoxyphenyl)sulfonium nonafluoro-n-butanesulfonate,

[0326] tri(p-methoxyphenyl)sulfonium perfluoro-n-octanesulfonate,

[0327] tri(p-methoxyphenyl)sulfonium pyrenesulfonate,

[0328] tri(p-methoxyphenyl)sulfonium n-dodecylbenzenesulfonate,

[0329] tri(p-methoxyphenyl)sulfonium p-toluenesulfonate,

[0330] tri(p-methoxyphenyl)sulfonium benzenesulfonate,

[0331] tri(p-methoxyphenyl)sulfonium 10-camphorsulfonate,

[0332] tri(p-methoxyphenyl)sulfonium n-octanesulfonate,

[0333] tri(p-methoxyphenyl)sulfonium

[0334] 2-trifluoromethylbenzenesulfonate,

[0335] tri(p-methoxyphenyl)sulfonium

[0336] 4-trifluoromethylbenzenesulfonate,

[0337] tri(p-methoxyphenyl)sulfonium perfluorobenzenesulfonate,

[0338] di(p-methoxyphenyl).p-tolylsulfonium

[0339] trifluoromethanesulfonate,

[0340] di(p-methoxyphenyl).p-tolylsulfonium

[0341] nonafluoro-n-butanesulfonate,

[0342] di(p-methoxyphenyl).p-tolylsulfonium

[0343] perfluoro-n-octanesulfonate,

[0344] di(p-methoxyphenyl).p-tolylsulfonium pyrenesulfonate,

[0345] di(p-methoxyphenyl).p-tolylsulfonium

[0346] n-dodecylbenzenesulfonate,

[0347] di(p-methoxyphenyl).p-tolylsulfonium p-toluenesulfonate,

[0348] di(p-methoxyphenyl).p-tolylsulfonium benzenesulfonate,

[0349] di(p-methoxyphenyl).p-tolylsulfonium 10-camphorsulfonate,

[0350] di(p-methoxyphenyl).p-tolylsulfonium n-octanesulfonate,

[0351] di(p-methoxyphenyl).p-tolylsulfonium

[0352] 2-trifluoromethylbenzenesulfonate,

[0353] di(p-methoxyphenyl).p-tolylsulfonium

[0354] 4-trifluoromethylbenzenesulfonate,

[0355] di(p-methoxyphenyl).p-tolylsulfonium

[0356] perfluorobenzenesulfonate,

[0357] phenyl.tetramethylenesulfonium trifluoromethanesulfonate,

[0358] phenyl.tetramethylenesulfonium

[0359] nonafluoro-n-butanesulfonate,

[0360] phenyl.tetramethylenesulfonium perfluoro-n-octanesulfonate,

[0361] phenyl.tetramethylenesulfonium pyrenesulfonate,

[0362] phenyl.tetramethylenesulfonium n-dodecylbenzenesulfonate,

[0363] phenyl.tetramethylenesulfonium p-toluenesulfonate,

[0364] phenyl.tetramethylenesulfonium benzenesulfonate,

[0365] phenyl.tetramethylenesulfonium 10-camphorsulfonate,

[0366] phenyl.tetramethylenesulfonium n-octanesulfonate,

[0367] phenyl.tetramethylenesulfonium

[0368] 2-trifluoromethylbenzenesulfonate,

[0369] phenyl.tetramethylenesulfonium

[0370] 4-trifluoromethylbenzenesulfonate,

[0371] phenyl.tetramethylenesulfonium perfluorobenzenesulfonate,

[0372] p-hydroxyphenyl.tetramethylenesulfonium

[0373] trifluoromethanesulfonate,

[0374] p-hydroxyphenyl.tetramethylenesulfonium

[0375] nonafluoro-n-butanesulfonate,

[0376] p-hydroxyphenyl.tetramethylenesulfonium

[0377] perfluoro-n-octanesulfonate,

[0378] p-hydroxyphenyl.tetramethylenesulfonium pyrenesulfonate,

[0379] p-hydroxyphenyl.tetramethylenesulfonium

[0380] n-dodecylbenzenesulfonate,

[0381] p-hydroxyphenyl.tetramethylenesulfonium p-toluenesulfonate,

[0382] p-hydroxyphenyl.tetramethylenesulfonium benzenesulfonate,

[0383] p-hydroxyphenyl.tetramethylenesulfonium

[0384] 10-camphorsulfonate,

[0385] p-hydroxyphenyl.tetramethylenesulfonium n-octanesulfonate,

[0386] p-hydroxyphenyl.tetramethylenesulfonium

[0387] 2-trifluoromethylbenzenesulfonate,

[0388] p-hydroxyphenyl.tetramethylenesulfonium

[0389] 4-trifluoromethylbenzenesulfonate,

[0390] p-hydroxyphenyl.tetramethylenesulfonium

[0391] perfluorobenzenesulfonate,

[0392] phenyl.biphenylenesulfonium trifluoromethanesulfonate,

[0393] phenyl.biphenylenesulfonium nonafluoro-n-butanesulfonate,

[0394] phenyl.biphenylenesulfonium perfluoro-n-octanesulfonate,

[0395] phenyl.biphenylenesulfonium pyrenesulfonate,

[0396] phenyl.biphenylenesulfonium n-dodecylbenzenesulfonate,

[0397] phenyl.biphenylenesulfonium p-toluenesulfonate,

[0398] phenyl.biphenylenesulfonium benzenesulfonate,

[0399] phenyl.biphenylenesulfonium 10o-camphorsulfonate,

[0400] phenyl.biphenylenesulfonium n-octanesulfonate,

[0401] phenyl.biphenylenesulfonium

[0402] 2-trifluoromethylbenzenesulfonate,

[0403] phenyl.biphenylenesulfonium

[0404] 4-trifluoromethylbenzenesulfonate,

[0405] phenyl.biphenylenesulfonium perfluorobenzenesulfonate,

[0406] (4-phenylthiophenyl).diphenylsulfonium

[0407] trifluoromethanesulfonate,

[0408] (4-phenylthiophenyl).diphenylsulfonium

[0409] nonafluoro-n-butanesulfonate,

[0410] (4-phenylthiophenyl).diphenylsulfonium

[0411] perfluoro-n-octanesulfonate,

[0412] (4-phenylthiophenyl).diphenylsulfonium pyrenesulfonate,

[0413] (4-phenylthiophenyl).diphenylsulfonium

[0414] n-dodecylbenzenesulfonate,

[0415] (4-phenylthiophenyl).diphenylsulfonium p-toluenesulfonate,

[0416] (4-phenylthiophenyl).diphenylsulfonium benzenesulfonate,

[0417] (4-phenylthiophenyl).diphenylsulfonium 10-camphorsulfonate,

[0418] (4-phenylthiophenyl).diphenylsulfonium n-octanesulfonate,

[0419] (4-phenylthiophenyl).diphenylsulfonium

[0420] 2-trifluoromethylbenzenesulfonate,

[0421] (4-phenylthiophenyl).diphenylsulfonium

[0422] 4-trifluoromethylbenzenesulfonate,

[0423] (4-phenylthiophenyl).diphenylsulfonium

[0424] perfluorobenzenesulfonate,

[0425] 4,4′-bis (diphenylsulfoniophenyl) sufide

[0426] di(trifluoromethanesulfonate),

[0427] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0428] di(nonafluoro-n-butanesulfonate),

[0429] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0430] di(perfluoro-n-octanesulfonate),

[0431] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0432] di(pyrenesulfonate),

[0433] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0434] di(n-dodecylbenzenesulfonate),

[0435] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0436] di(p-toluenesulfonate),

[0437] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0438] di(benzenesulfonate),

[0439] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0440] di(10-camphorsulfonate),

[0441] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0442] di(n-octanesulfonate),

[0443] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0444] di(2-trifluoromethylbenzenesulfonate),

[0445] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0446] di(4-trifluoromethylbenzenesulfonate),

[0447] 4,4′-bis(diphenylsulfoniophenyl)sulfide

[0448] di(perfluorobenzenesulfonate),

[0449] and the like.

[0450] (2) Sulfone compounds

[0451] As examples of sulfone compounds, β-ketosulfone,β-sulfonylsulfone, and α-diazo compounds of these compounds can begiven.

[0452] As specific examples of sulfone compounds, phenacylphenylsulfone,mesitylphenacylsulfone, bis(phenylsulfonyl)methane, and4-trisphenacylsulfone can be given.

[0453] (3) Sulfonate compounds

[0454] As examples of sulfonate compounds, alkyl sulfonate, haloalkylsulfonate, aryl sulfonate, and imino sulfonate can be given.

[0455] As specific examples of sulfonate compounds, benzointosylate,pyrogallol tris (trifluoromethanesulfonate), pyrogalloltris(nonafluorobutanesufonate), pyrogallol tris(methanesulfonate),nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate,α-methylolbenzointosylate, α-methylolbenzoin trifluoromethanesulfonate,α-methylolbenzoin n-octanesulfonate, and α-methylolbenzoinn-dodecanesulfonate can be given.

[0456] (4) Sulfonimide compounds

[0457] As examples of sulfonimide compounds, compounds of the followingformula (2) can be given:

[0458] wherein R⁴represents a divalent group such as an alkylene group,arylene group, and alkoxylene group, and R⁵ represents a monovalentgroup such as an alkyl group, aryl group, halogenated alkyl group, andhalogenated aryl group.

[0459] Specific examples of sulfonimide compounds include:

[0460] N-(trifluoromethanesulfonyloxy)succinimide,

[0461] N-(trifluoromethanesulfonyloxy)phthalimide,

[0462] N-(trifluoromethanesulfonyloxy)diphenylmaleimide,

[0463] N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]

[0464] hept-5-ene-2,3-dicarboxyimide,

[0465] N-(trifluoromethanesulfonyloxy)-7-oxabicyclo[2.2.1]

[0466] hept-5-ene-2,3-dicarboxyimide,

[0467] N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]

[0468] heptan-5,6-oxy-2,3-dicarboxyimide,

[0469] N-(trifluoromethanesulfonyloxy)naphthylimide,

[0470] N-(10-camphorsulfonyloxy)succinimide,

[0471] N-(10-camphorsulfonyloxy)phthalimide,

[0472] N-(10-camphorsulfonyloxy)diphenylmaleimide,

[0473] N-(10-camphorsulfonyloxy)bicyclo[2.2.1]

[0474] hept-5-ene-2,3-dicarboxyimide,

[0475] N-(10-camphorsulfonyloxy)-7-oxabicyclo[2.2.1]

[0476] hept-5-ene-2,3-dicarboxyimide,

[0477] N-(10-camphorsulfonyloxy)bicyclo[2.2.1]

[0478] heptan-5,6-oxy-2,3-dicarboxyimide,

[0479] N-(10-camphorsulfonyloxy)naphthylimide,

[0480] N-(n-octanesulfonyloxy)succinimide,

[0481] N-(n-octanesulfonyloxy)phthalimide,

[0482] N-(n-octanesulfonyloxy)diphenylmaleimide,

[0483] N-(n-octanesulfonyloxy)bicyclo[2.2.1]

[0484] hept-5-ene-2,3-dicarboxyimide,

[0485] N-(n-octanesulfonyloxy)-7-oxabicyclo[2.2.1]

[0486] hept-5-ene-2,3-dicarboxyimide,

[0487] N-(n-octanesulfonyloxy)bicyclo[2.2.1]

[0488] heptan-5,6-oxy-2,3-dicarboxyimide,

[0489] N-(n-octanesulforiyloxy)naphthylimide,

[0490] N-(p-toluenesulfonyloxy)succinimide,

[0491] N-(p-toluenesulfonyloxy)phthalimide,

[0492] N-(p-toluenesulfonyloxy)diphenylmaleimide,

[0493] N-(p-toluenesulfonyloxy)bicyclo[2.2.1]

[0494] hept-5-ene-2,3-dicarboxyimide,

[0495] N-(p-toluenesulfonyloxy)-7-oxabicyclo[2.2.1]

[0496] hept-5-ene-2,3-dicarboxyimide,

[0497] N-(p-toluenesulfonyloxy)bicyclo[2.2.1]

[0498] heptan-5,6-oxy-2,3-dicarboxyimide,

[0499] N-(p-toluenesulfonyloxy)naphthylimide,

[0500] N-(2-trifluoromethylbenzenesulfonyloxy)succinimide,

[0501] N-(2-trifluoromethylbenzenesulfonyloxy)phthalimide,

[0502] N-(2-trifluoromethylbenzenesulfonyloxy)diphenylmaleimide,

[0503] N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]

[0504] hept-5-ene-2,3-dicarboxyimide,

[0505] N-(2-trifluoromethylbenzenesulfonyloxy)-7-oxabicyclo[2.2.1]

[0506] hept-5-ene-2,3-dicarboxyimide,

[0507] N-(2-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]

[0508] heptane-5,6-oxy-2,3-dicarboxyimide,

[0509] N-(2-trifluoromethylbenzenesulfonyloxy)naphthylimide,

[0510] N-(4-trifluoromethylbenzenesulfonyloxy)succinimide,

[0511] N-(4-trifluoromethylbenzenesulfonyloxy)phthalimide,

[0512] N-(4-trifluoromethylbenzenesulfonyloxy)diphenylmaleimide,

[0513] N-(4-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]

[0514] hept-5-ene-2,3-dicarboxyimide,

[0515] N-(4-trifluoromethylbenzenesulfonyloxy)-7-oxabicyclo[2.2.1]

[0516] hept-5-ene-2,3-dicarboxyimide,

[0517] N-(4-trifluoromethylbenzenesulfonyloxy)bicyclo[2.2.1]

[0518] heptane-5,6-oxy-2,3-dicarboxyimide,

[0519] N-(4-trifluoromethylbenzenesulfonyloxy)naphthylimide,

[0520] N-(perfluorobenzenesulfonyloxy)succinimide,

[0521] N-(perfluorobenzenesulfonyloxy)phthalimide,

[0522] N-(perfluorobenzenesulfonyloxy)diphenylmaleimide,

[0523] N-(perfluorobenzenesulfonyloxy)bicyclo[2.2.1]

[0524] hept-5-ene-2, 3-dicarboxyimide,

[0525] N-(perfluorobenzenesulfonyloxy)-7-oxabicyclo[2.2.1]

[0526] hept-5-ene-2,3-dicarboxyimide,

[0527] N-(perfluorobenzenesulfonyloxy)bicyclo[2.2.1]

[0528] heptan-5,6-oxy-2,3-dicarboxyimide,

[0529] N-(perfluorobenzenesulfonyloxy)naphthylimide,

[0530] N-(naphthalenesulfonyloxy)succinimide,

[0531] N-(naphthalenesulfonyloxy)phthalimide,

[0532] N-(naphthalenesulfonyloxy)diphenylmaleimide,

[0533] N-(naphthalenesulfonyloxy)bicyclo[2.2.1]

[0534] hept-5-ene-2,3-dicarboxyimide,

[0535] N-(naphthalenesulfonyloxy)-7-oxabicyclo[2.2.1]

[0536] hept-5-ene-2,3-dicarboxyimide,

[0537] N-(naphthalenesulfonyloxy)bicyclo[2.2.1]

[0538] heptan-5,6-oxy-2,3-dicarboxyimide,

[0539] N-(naphthalenesulfonyloxy)naphthylimide,

[0540] N-(nonafluoro-n-butanesulfonyloxy)succinimide,

[0541] N-(nonafluoro-n-butanesulfonyloxy)phthalimide,

[0542] N-(nonafluoro-n-butanesulfonyloxy)diphenylmaleimide,

[0543] N-(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]

[0544] hept-5-ene-2,3-dicarboxyimide,

[0545] N-(nonafluoro-n-butanesulfonyloxy)-7-oxabicyclo[2.2.1]

[0546] hept-5-ene-2,3-dicarboxyimide,

[0547] N-(nonafluoro-n-butanesulfonyloxy)bicyclo[2.2.1]

[0548] heptan-5,6-oxy-2,3-dicarboxyimide,

[0549] N-(nonafluoro-n-butanesulfonyloxy)naphthylimide,

[0550] N-(perfluoro-n-octanesulfonyloxy) succinimide,

[0551] N-(perfluoro-n-octanesulfonyloxy)phthalimide,

[0552] N-(perfluoro-n-octanesulfonyloxy)diphenylmaleimide,

[0553] N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]

[0554] hept-5-ene-2,3-dicarboxyimide,

[0555] N-(perfluoro-n-octanesulfonyloxy)-7-oxabicyclo[2.2.1]

[0556] hept-5-ene-2,3-dicarboxyimide,

[0557] N-(perfluoro-n-octanesulfonyloxy)bicyclo[2.2.1]

[0558] heptan-5,6-oxy-2,3-dicarboxyimide,

[0559] N-(perfluoro-n-octanesulfonyloxy)naphthylimide,

[0560] N-(benzenesulfonyloxy)succinimide,

[0561] N-(benzenesulfonyloxy)phthalimide,

[0562] N-(benzenesulfonyloxy)diphenylmaleimide,

[0563] N-(benzenesulfonyloxy)bicyclo[2.2.1]

[0564] hept-5-ene-2,3-dicarboxyimide,

[0565] N-(benzenesulfonyloxy)-7-oxabicyclo[2.2.1]

[0566] hept-5-ene-2,3-dicarboxyimide,

[0567] N-(benzenesulfonyloxy)bicyclo[2.2.1]

[0568] heptan-5,6-oxy-2,3-dicarboxyimide,

[0569] N-(benzenesulfonyloxy)naphthylimide, and the like.

[0570] (5) Disulfonyldiazomethane compounds

[0571] As examples of disulfonyldiazomethane compounds, a compound shownby the following formula (3) can be given:

[0572] wherein R⁶ and R⁷ individually represent a monovalent group suchas an alkyl group, aryl group, halogenated alkyl group, and halogenatedaryl group.

[0573] The following compounds can be given as specific examples ofdisulfonyldiazomethane compounds:

[0574] bis (trifluoromethanesulfonyl) diazomethane,

[0575] bis (cyclohexanesulfonyl) diazomethane,

[0576] bis (phenylsulfonyl) diazomethane,

[0577] bis (p-toluenesulfonyl) diazomethane,

[0578] bis (2, 4-dimethylbenzenesulfonyl) diazomethane,

[0579] methylsulfonyl-p-toluenesulfonyldiazomethane,

[0580] bis(p-t-butylphenylsulfonyl)diazomethane,

[0581] bis(p-chlorobenzenesulfonyl)diazomethane,

[0582] cyclohexylsulfonyl p-toluenesulfonyldiazomethane,

[0583] 1-cyclohexylsulfonyl 1,l-dimethylethylsulfonyldiazomethane

[0584] bis(1,1-dimethylethylsulfonyl)diazomethane,

[0585] bis(1-methylethylsulfonyl)diazomethane,

[0586]bis(3,3-dimethyl-1,5-dioxaspiro[5.5]dodecane-8-sulfonyl)-diazomethane,and

[0587] bis(1,4-dioxaspiro[4.5]decane-7-sulfonyl)diazomethane.

[0588] (6) Disulfonylmethane compounds

[0589] As examples of disulfonylmethane compounds, a compound of thefollowing formula (4) can be given:

[0590] wherein R⁸ and R⁹ individually represent a linear or branchedmonovalent aliphatic hydrocarbon group, cycloalkyl group, aryl group,aralkyl group, or other monovalent organic group having a hetero atom,and V and W individually represent an aryl group, a hydrogen atom, alinear or branched monovalent aliphatic hydrocarbon group, or amonovalent organic group having a hetero atom, provided that at leastone of V and W represents an aryl group, or V and W bond to form amono-carbocyclic or poly-carbocyclic structure having at least oneunsaturated bond, or V and W bond to form a group of the followingformula:

[0591] wherein V′ and W′ individually represent a hydrogen atom, halogenatom, linear or branched alkyl group, cycloalkyl group, aryl group, oraralkyl group, or V′ and W′, each bonding to the same or differentcarbon atoms, bond to form a mono-carbocyclic structure, and n is aninteger of 2-10.

[0592] (7) Oxime sulfonate compounds

[0593] As examples of oxime sulfonate compounds, compounds of thefollowing formula (5) or (6) can be given:

[0594] wherein R¹⁰ and R¹¹ individually represent a monovalent organicgroup,

[0595] wherein R¹², R¹³, R¹⁴, and R¹⁵ individually represent amonovalent organic group.

[0596] As specific preferable examples of R¹⁰ in the formula (5), amethyl group, ethyl group, n-propyl group, phenyl group, tosyl group,trifluoromethyl group, and pentafluoroethyl group can be given. Aspreferable examples of R¹¹, a phenyl group, tosyl group, and 1-naphthylgroup can be given.

[0597] As specific preferable examples of R¹² and R ³in the formula (6),a methyl group, ethyl group, n-propyl group, phenyl group, tosyl group,trifluoromethyl group, and pentafluoroethyl group can be given. Aspreferable examples of R¹⁴ and R¹⁵, a phenyl group, tosyl group, and1-naphthyl group can be given.

[0598] (8) Hydrazine sulfonate compounds

[0599] As specific examples of hydrazine sulfonate compounds,

[0600] bis(benzenesulfonyl)hydrazine,

[0601] bis(p-toluenesulfonyl)hydrazine,

[0602] bis(trifluoromethanesulfonyl)hydrazine,

[0603] bis(pentafluoroethanesulfonyl)hydrazine,

[0604] bis(n-propanesulfonyl)hydrazine, benzenesulfonylhydrazine,

[0605] p-toluenesulfonylhydrazine,

[0606] trifluoromethanesulfonylhydrazine,

[0607] pentafluoroethanesulfonylhydrazine,

[0608] n-propanesulfonylhydrazine, and

[0609] trifluoromethanesulfonyl.p-toluenesulfonylhydrazine can be given.

[0610] The acid generator (C) can be used either individually or incombination of two or more in the chemically amplified radiationsensitive resin composition [I].

[0611] The amount of the acid generator (C) used is preferably 0.1-20parts by weight, and still more preferably 0.5-15 parts by weight, for100 parts by weight of the acid-dissociable group-containing resin (B).

[0612] Acid diffusion controller

[0613] It is preferable to add an acid diffusion controller to thechemically amplified radiation sensitive resin composition [I]. The aciddiffusion controller controls diffusion of an acid generated from theacid generator (C) upon exposure in the resist film to hinderunfavorable chemical reactions in the unexposed area.

[0614] The addition of the acid diffusion controller improves storagestability of the composition and resolution as a resist. Moreover, theaddition of the acid diffusion controller prevents the line width of theresist pattern from changing due to variation of post-exposure delay(PED) from exposure to post-exposure heat treatment, whereby acomposition with remarkably superior process stability can be obtained.

[0615] As the acid diffusion controller, organic compounds containingnitrogen of which the basicity does not change during exposure orheating for forming a resist pattern are preferable.

[0616] As examples of such nitrogen-containing organic compounds, acompound shown by the following formula (7) (hereinafter called“nitrogen-containing compound (α)”),

[0617] wherein R¹⁶, R¹⁷, and R¹⁸ individually represent a hydrogen atom,a substituted or unsubstituted alkyl group, substituted or unsubstitutedaryl group, or substituted or unsubstituted aralkyl group, a diaminocompound having two nitrogen atoms in the molecule (hereinafter referredto as “nitrogen-containing compound (β)”), a diamino polymer havingthree or more nitrogen atoms in the molecule (hereinafter referred to as“nitrogen-containing compound (γ)”), an amide group-containing compound,urea compound, and nitrogen-containing heterocyclic compound can begiven.

[0618] As examples of the nitrogen-containing compounds (α), linear,branched, orcyclicmonoalkylamines such as n-hexylamine, n-heptylamine,n-octylamine, n-nonylamine, n-decylamine, and cyclohexylamine;dialkylamines such as di-n-butylamine, di-n-pentylamine,di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine,di-n-decylamine, methyl-cyclohexylamine, and dicyclohexylamine; linear,branched, or cyclic trialkylamines such as triethylamine,tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine,tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine,tri-n-decylamine, cyclohexyldimethylamine, methyldicyclohexylamine, andtricyclohexylamine; and aromatic amines such as aniline,N-methylaniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline,4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, andnaphthylamine can be given.

[0619] Examples of the nitrogen-containing compounds (β) includeethylenediamine, N,N,N′,N′-tetramethylethylenediamine,N,N,N′,N′-tetrakis(2-hydroxypropyl)ethylenediamine,tetramethylenediamine, hexamethylenediamine,4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether,4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine,2,2′-bis(4-aminophenyl)propane,2-(3-aminophenyl)-2-(4-aminophenyl)propane,2-(4-aminophenyl)-2-(3-hydroxyphenyl)propane,2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane,1,4-bis[1-(4-aminophenyl)-1-methylethyl]benzene, and1,3-bis[1-(4-aminophenyl)-1-methylethyl]benzene.

[0620] Examples of the nitrogen-containing compounds (γ) includepolyethyleneimine, polyallylamine, and a polymer ofN-(dimethylaminoethyl)acrylamide.

[0621] Examples of compounds containing an amide group includeformamide, N-methylformamide, N,N-dimethylformamide, acetamide,N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide,pyrrolidone, and N-methylpyrrolidone.

[0622] Examples of urea compounds include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea,1,3-diphenylurea, and tributylthiourea.

[0623] Examples of the nitrogen-containing heterocyclic compoundsinclude imidazoles such as imidazole, benzimidazole, 4-methylimidazole,4-methyl-2-phenylimidazole, and 2-phenylbenzimidazole; pyridines such aspyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine,4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine,2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide,quinoline, 8-oxyquinoline, and acridine; pyrazine, pyrazole, pyridazine,quinoxaline, purine, pyrrolidine, piperidine, morpholine,4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, and1,4-diazabicyclo[2.2.2]octane.

[0624] Base precursors possessing an acid-dissociable group, such asN-(t-butoxycarbonyl)piperidine, N-(t-butoxycarbonyl)imidazole,N-(t-butoxycarbonyl)benzimidazole,N-(t-butoxycarbonyl)-2-phenylbenzimidazole, N-(t-butoxycarbonyl)di-n-octylamine, N- (t-butoxy carbonyl)diethanolamine, N-(t-butoxycarbonyl)dicyclohexylamine, andN-(t-butoxycarbonyl)diphenylamine can be used as nitrogen-containingorganic compounds acting as an acid diffusion controller.

[0625] Of these nitrogen-containing organic compounds, thenitrogen-containing compound (α) and the nitrogen-containingheterocyclic compound are preferable. Trialkylamines are particularlypreferable among the nitrogen-containing compound (α), and pyridines areparticularly preferable among the nitrogen-containing heterocycliccompounds.

[0626] The acid diffusion controller may be used either individually orin combination of two or more.

[0627] The amount of the acid diffusion controller to be added isusually 15 parts by weight or less, preferably 0.001-10 parts by weight,and still more preferably 0.005-5 parts by weight for 100 parts byweight of the acid-dissociable group-containing resin (B). If theproportion of the acid diffusion controller exceeds 15 parts by weight,sensitivity as a resist and developability of the exposed area tend todecrease. If the proportion is less than 0.001 part by weight, accuracyof pattern profiles and dimensions as a resist may decrease depending onprocessing conditions.

[0628] Surfactant

[0629] Surfactants exhibiting an action of improving the applicabilityor striation of the composition and developability as a resist may beadded to the radiation-sensitive resin composition [I].

[0630] Examples of such surfactants include polyoxyethylene laurylether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether,polyoxyethylene n-octyl phenol ether, polyoxyethylene n-nonyl phenolether, polyethylene glycol dilaurate, polyethylene glycol distearate;and commercially available products such as FTOPEF301, EF303, EF352(manufactured by TOHKEM PRODUCTS CORPORATION), MEGAFAC F171, F173(manufactured by Dainippon Ink and Chemicals, Inc.), Fluorad FC430,FC431 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, SurflonS-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured byAsahi Glass Co., Ltd.), KP341 (manufactured by Shin-Etsu Chemical Co.,Ltd.), and Polyflow No. 75, No. 95 (manufactured by Kyoeisha ChemicalCo., Ltd.).

[0631] These surfactants may be used either individually or incombination of two or more. The amount of the surfactants to be added isusually 2 parts by weight or less for 100 parts by weight of theacid-dissociable group-containing resin (B).

[0632] Other sensitizer

[0633] Sensitizers other than the carbazole derivative (1) can be addedto the composition of the present invention (such sensitizers arehereinafter referred to as “other acid sensitizers”).

[0634] As preferable examples of the other sensitizers, benzophenones,rose bengals, and anthracenes can be given.

[0635] These other sensitizers may be used either individually or incombination of two or more. The amount of the other sensitizers to beadded is usually 50 parts by weight or less for 100 parts by weight ofthe acid-dissociable group-containing resin (B).

[0636] Other additives

[0637] A dye and/or a pigment may be added to visualize latent images ofexposed areas and to reduce the effect of halation during exposure. Anadhesion adjuvant may be added to improve adhesiveness to the substrate.

[0638] Halation inhibitors such as 4-hydroxy-4′-methylchalcone, formimprovers, preservation stabilizers, antifoaming agents, and the likecan also be added.

[0639] Solvent

[0640] When used, the radiation-sensitive resin composition [1] isusually prepared into a composition solution by homogeneously dissolvingthe composition in a solvent so that the total solid concentration is0.1-50 wt %, and preferably 1-40 wt %, and filtering the solution usinga filter with a pore diameter of about 0.2 μm.

[0641] As examples of a solvent used for preparing the above compositionsolution, ethylene glycol monoalkyl ether acetates such as ethyleneglycol monomethyl ether acetate, ethylene glycol monoethyl etheracetate, ethylene glycol mono-n-propyl ether acetate, and ethyleneglycol mono-n-butyl ether acetate; propylene glycol monoalkyl etherssuch as propylene glycol monomethyl ether, propylene glycol monoethylether, propylene glycol mono-n-propyl ether, and propylene glycolmono-n-butyl ether; propylene glycol dialkyl ethers such as propyleneglycol dimethyl ether, propylene glycol diethyl ether, propylene glycoldi-n-propyl ether, and propylene glycol di-n-butyl ether; propyleneglycol monoalkyl ether acetates such as propylene glycol monomethylether acetate, propylene glycol monoethyl ether acetate, propyleneglycol mono-n-propyl ether acetate, and propylene glycol mono-n-butylether acetate; lactic acid esters such as methyl lactate, ethyl lactate,n-propyl lactate, and i-propyl lactate; aliphatic carboxylic acid esterssuch as n-amyl formate, i-amyl formate, ethyl acetate, n-propyl acetate,i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate,i-amyl acetate, i-propyl propionate, n-butyl propionate, and i-butylpropionate; other esters such as ethyl hydroxyacetate, ethyl2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, ethylmethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl3-methoxypropionate, methyl 3-ethoxypropionate, ethyl3-ethoxypropionate, butyl 3-methoxyacetate, butyl3-methyl-3-methoxyacetate, butyl 3-methyl-3-methoxypropionate, butyl3-methyl-3-methoxybutyrate, methyl acetoacetate, ethyl acetoacetate,methyl pyruvate, and ethyl pyruvate; aromatic hydrocarbons such astoluene and xylene; ketones such as methyl ethyl ketone, 2-pentanone,2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone;amides such as N-methylformamide, N,N-dimethylformamide,N-methylacetamide, N,N-dimethyl acetamide, and N-methylpyrrolidone; andlactones such as γ-butyrolactone can be given.

[0642] These solvents may be used either individually or in combinationsof two or more.

[0643] Formation of resist pattern

[0644] A resist pattern is formed from the radiation-sensitive resincomposition [I] by applying the composition solution prepared asmentioned above to substrates such as a silicon wafer or a wafer coveredwith aluminum using an appropriate application method such as rotationalcoating, cast coating, and roll coating to form a resist film. Theresist film is then optionally heated at a temperature of about 70-160°C. (hereinafter referred to as “PB”) and exposed to light through apredetermined mask pattern.

[0645] Radiation used here can be appropriately selected according tothe types of acid generator (C) from among deep ultraviolet rays such asa KrF excimer laser (wavelength: 248 nm), ArF excimer laser (wavelength:193 nm), or F₂ excimer laser (wavelength: 157 nm), X-rays such assynchrotron radiation, and charged particle rays such as electron beams.

[0646] The exposure conditions such as the amount of exposure areappropriately determined depending on the composition of theradiation-sensitive resin composition [I], types of additives, and thelike.

[0647] In the present invention, it is preferable to performpost-exposure bake (hereinafter referred to as“PEB”) at70-160° C. for 30seconds or more in order to steadily form a minute resist pattern withhigh precision. If the heating temperature for PEB is less than 70° C.,sensitivity may fluctuate according to the type of substrates.

[0648] A desired resist pattern is obtained by developing the resistusing an alkaline developer at 10-50° C. for 10-200 seconds, preferablyat 15-30° C. for 15-100 seconds, and still more preferably at 20-25° C.for 15-90 seconds.

[0649] As the alkaline developer, an alkaline aqueous solution preparedby dissolving an alkali such as an alkali metal hydroxide, aqueousammonia, mono-, di-, or tri-alkylamine, mono-, di-, or tri-alkanolamine,heterocyclic amine, tetraalkylammonium hydroxide, choline,1,8-diazabicyclo[5.4.0]-7-undecene, or 1,5-diazabicyclo [4.3.0]-5-noneneto a concentration of 1-10 wt %, preferably 1-5 wt %, and particularlypreferably 1-3 wt % can be used.

[0650] Moreover, an appropriate amount of a water-soluble organicsolvent such as methanol and ethanol or a surfactant can be added to thedeveloper comprising the above alkaline aqueous solution.

[0651] When forming a resist pattern, a protective film may be providedon the resist film in order to prevent an adverse effect of basicimpurities and the like which are present in the environmentalatmosphere.

EXAMPLES

[0652] The embodiments of the present invention are described in moredetail by examples. However, these examples should not be construed aslimiting the present invention.

[0653] <Synthesis of carbazole derivative (1)>

Synthesis Example 1

[0654] 100 g of carbazole, 83 g of bromoacetic acid, and 134 g oft-butoxy potassium were reacted in 1,000 g of dimethylformamideovernight at room temperature. After the addition of 300 g of 5 wt %oxalic acid aqueous solution, the reaction mixture was extracted withn-hexane. Precipitate obtained by crystallization in a mixed solvent ofdimethylformamide and n-hexane was dried under vacuum to obtain 56 g ofcarbazole derivative (1) of the formula (1-1) as a white solid.

[0655] This compound is referred to as a “carbazole derivative (1)(A-1)”.

Synthesis Example 2

[0656] 100 g of carbazole, 117 g of bromoacetic acid, and 67 g oft-butoxy potassium were reacted in 1,000 g of dimethyl formamide overnight at room temperature. The reaction mixture was processed in thesame manner as in the Synthesis Example 1 to obtain 79g of carbazolederivative (1) of the formula (1-7) as a white solid.

[0657] IR absorption spectrum and ¹H-NMR spectrum of this compound arerespectively shown in FIG. 1 and FIG. 2. The UV absorption spectrum ofthis compound was measured and shown in FIG. 3. The UV absorptionspectrum indicates a particularly strong absorption around thewavelength of 200-250 nm.

[0658] This compound is referred to as a “carbazole derivative (1)(A-2)”.

Synthesis Example 3

[0659] 100 g of carbazole, 137 g of benzyl bromoacetate, and 67 g oft-butoxy potassium were reacted in 1,000 g of dimethyl formamideovernight at room temperature. The reaction mixture was processed in thesame manner as in the Synthesis Example 1 to obtain 85 g of carbazolederivative (1) of the formula (1-10) as a white solid.

[0660] This compound is referred to as a “carbazole derivative (1)(A-3)”.

Synthesis Example 4

[0661] 100 g of carbazole, 108 g of i-propyl bromoacetate, and 67 g oft-butoxy potassium were reacted in 1,000 g of dimethyl formamideovernight at room temperature. The reaction mixture was processed in thesame manner as in the Synthesis Example 1 to obtain 62g of carbazolederivative (1) of the formula (1-6) as a white solid.

[0662] This compound is referred to as a “carbazole derivative (1)(A-4)”.

Synthesis Example 5

[0663] 100 g of carbazole, 132 g of cyclohexyl bromoacetate, and 67 g oft-butoxy potassium were reacted in 1,000 g of dimethyl formamideovernight at room temperature. The reaction mixture was processed in thesame manner as in the Synthesis Example 1 to obtain 99g of carbazolederivative (1) of the formula (1-8) as a white solid.

[0664] This compound is referred to as a “carbazole derivative (1)(A-5)”.

Synthesis Example 6

[0665] 100 g of carbazole, 125 g of t-butyl 2-bromopropionate, and 67 gof t-butoxy potassium were reacted in 1,000 g of dimethyl formamideovernight at room temperature. The reaction mixture was processed in thesame manner as in the Synthesis Example 1 to obtain 85g of carbazolederivative (1) of the formula (1-20) as a white solid.

[0666] This compound is referred to as a “carbazole derivative (1)(A-6)”.

Synthesis Example 7

[0667] 100g of carbazole, 149g of cyclohexyl 2-bromoisobutyrate, and 67g of t-butoxy potassium were reacted in 1,000 g of dimethyl formamideovernight at room temperature. The reaction mixture was processed in thesame manner as in the Synthesis Example 1 to obtain 105 g of carbazolederivative (1) of the formula (1-34) as a white solid.

[0668] This compound is referred to as a “carbazole derivative (1)(A-7)”.

Synthesis Example 8

[0669] 100 g of carbazole, 173 g of cyclohexylα-bromocyclohexanecarboxylate, and 67 g of t-butoxy potassium werereacted in 1,000 g of dimethylformamide overnight at room temperature.The reaction mixture was processed in the same manner as in theSynthesis Example 1 to obtain 105 g of carbazole derivative (1) of theformula (1-73) as a white solid.

[0670] This compound is referred to as a “carbazole derivative (1)(A-8)”.

[0671] <Preparation of acid-dissociable group-containing resin (B)>

[0672] Mw and Mn of the resins prepared in Synthesis Examples 9-18 weremeasured by gel permeation chromatography (GPC) using GPC columns(manufactured by Tosoh Corp., G2000H_(XL×)2, G3000H_(XL)×1,G4000H_(XL)×1) under the following conditions. Flow rate: 1.0 ml/minute,eluate: tetrahydrofuran, column temperature: 40°C., standard referencematerial: monodispersed polystyrene

Synthesis Example 9

[0673] 101 g of p-acetoxystyrene, 5 g of styrene, 42 g ofp-t-butoxystyrene, 6 g of azobisisobutyronitrile, and 1 g oft-dodecylmercaptan were dissolved in 160 g of propylene glycolmonomethyl ether. The mixture was polymerized at 70° C. for 16 hours ina nitrogen atmosphere. After the polymerization, the reaction solutionwas added dropwise to a large quantity of n-hexane to coagulate andpurify the resulting resin.

[0674] After the addition of 150 g of propylene glycol monomethyl etherto the resin, 300 g of methanol, 80 g of triethylamine, and 15 g ofdistilled water were added. The mixture was hydrolyzed for 8 hours whilerefluxing at the boiling point. After the reaction, the solvent andtriethylamine were evaporated under reduced pressure. The resultingresin was dissolved in acetone and added dropwise to a large quantity ofdistilled water to coagulate the resin. The resulting white powder wasfiltered and dried overnight at 50° C. under reduced pressure.

[0675] The resin was found to have Mw and Mw/Mn of 16,000 and 1.7respectively. The result of ¹³C-NMR analysis confirmed that the resinwas a copolymer of p-hydroxystyrene, styrene, and p-t-butoxystyrene at acopolymerization molar ratio of 72:5:23.

[0676] This resin is referred to as “acid-dissociable group-containingresin (B-1)”.

Synthesis Example 10

[0677] 100 g of p-acetoxystyrene, 25 g of t-butyl acrylate, 18 g ofstyrene, 6 g of azobisisobutyronitrile, and 1 g of t-dodecylmercaptanwere dissolved in 230 g of propylene glycol monomethyl ether. Themixture was polymerized at 70° C. for 16 hours in a nitrogen atmosphere.After the polymerization, the reaction solution was added dropwise to alarge quantity of n-hexane to coagulate and purify the resulting resin.

[0678] After the addition of 150 g of propylene glycol monomethyl etherto the resin, 300 g of methanol, 80 g of triethylamine, and 15 g ofdistilled water were added. The mixture was hydrolyzed for 8 hours whilerefluxing at the boiling point. After the reaction, the solvent andtriethylamine were evaporated under reduced pressure. The resultingresin was dissolved in acetone and added dropwise to a large quantity ofdistilled water to coagulate the resin. The resulting white powder wasfiltered and dried overnight at 50° C. under reduced pressure.

[0679] The resin was found to have Mw and Mw/Mn of 11,500 and 1.6respectively. The result of ¹³C-NMR analysis confirmed that the resinwas a copolymer of p-hydroxystyrene, t-butyl acrylate, and styrene at acopolymerization molar ratio of 61:19:20.

[0680] This resin is referred to as “acid-dissociable group-containingresin (B-2)”.

Synthesis Example 11

[0681] 125 g of p-acetoxystyrene, 20 g of t-butyl acrylate, 10 g ofstyrene, 8 g of 2,5-dimethylhexane-2,5-diacrylate, 8 g ofazobisisobutyronitrile, and 6 g of t-dodecylmercaptan were dissolved in170 g of propylene glycol monomethyl ether. The mixture was polymerizedfor 16 hours at 70° C. in a nitrogen atmosphere. After thepolymerization, the reaction solution was added dropwise to a largequantity of n-hexane to coagulate and purify the resulting resin.

[0682] After the addition of 150 g of propylene glycol monomethyl etherto the resin, 300 g of methanol, 80 g of triethylamine, and 15 g ofdistilled water were added. The mixture was hydrolyzed for 8 hours whilerefluxing at the boiling point. After the reaction, the solvent andtriethylamine were evaporated under reduced pressure. The resultingresin was dissolved in acetone and added dropwise to a large quantity ofdistilled water to coagulate the resin. The resulting white powder wasfiltered and dried overnight at 50° C. under reduced pressure.

[0683] The resin was found to have Mw and Mw/Mn of 40,000 and 2.6,respectively. The result of¹³C-NMR analysis confirmed that the resin wasa copolymer of p-hydroxystyrene, t-butyl acrylate, styrene, and 2,5-dimethylhexane-2,5-diacrylate at a copolymerization molar ratio of72:10:15:3.

[0684] This resin is referred to as “acid-dissociable group-containingresin (B-3)”.

Synthesis Example 12

[0685] 140 g of p-acetoxystyrene, 50 g of p-t-butoxystyrene, 9 g of2,5-dimethylhexane-2,5-diacrylate, 8 g of azobisisobutyronitrile, and 6g of t-dodecylmercaptan were dissolved in 240 g of propylene glycolmonomethyl ether. The mixture was polymerized for 16 hours at 70° C. ina nitrogen atmosphere. After the polymerization, the reaction solutionwas added dropwise to a large quantity of n-hexane to coagulate andpurify the resulting resin.

[0686] After the addition of 150 g of propylene glycol monomethyl etherto the resin, 300 g of methanol, 100 g of triethylamine, and 15 g ofdistilled water were added. The mixture was hydrolyzed for 8 hours whilerefluxing at the boiling point. After the reaction, the solvent andtriethylamine were evaporated under reduced pressure. The resultingresin was dissolved in acetone and added dropwise to a large quantity ofdistilled water to coagulate the resin. The resulting white powder wasfiltered and dried overnight at 50° C. under reduced pressure.

[0687] The resin was found to have Mw and Mw/Mn of 40,000 and 2.6,respectively. The result of ¹³C-NMR analysis confirmed that the resinwas a copolymer of p-hydroxystyrene, p-t-butoxystyrene, and2,5-dimethylhexane-2,5-diacrylate at a copolymerization molar ratio of67:30:3.

[0688] This resin is referred to as “acid-dissociable group-containingresin (B-4)”.

Synthesis Example 13

[0689] 176 g of p-t-butoxystyrene was anionically polymerized at −78° C.in 500 ml of tetrahydrofuran using n-butyllithium as acatalyst. Thereaction solution was added dropwise to methanol to coagulate, therebyobtaining 150g of poly(p-t-butoxystyrene) as a white solid.

[0690] The poly(p-t-butoxystyrene) was dissolved in 600 g of dioxane.After the addition of diluted hydrochloric acid, the mixture washydrolyzed at 70° C. for2hours. There action product was caused tocoagulate by adding to a large quantity of distilled water, therebyobtaining a white resin. Then, a step of dissolving the resulting resinin acetone and adding the solution dropwise to a large quantity ofdistilled water to coagulate the resin was repeated. The resulting whitepowder was filtered and dried overnight at 50° C. under reducedpressure.

[0691] The Mw and Mw/Mn of this resin were 10,400 and 1.10,respectively. ¹³C-NMR analysis confirmed that the resin is a copolymerof p-t-butoxystyrene and p-hydroxystyrene at a copolymerization molarratio of these monomers of 68:32, in which part of t-butyl group in thepoly(p-t-butoxystyrene) had a hydrolyzed structure.

[0692] This resin is referred to as “acid-dissociable group-containingresin (B-5)”.

Synthesis Example 14

[0693] 7 g of di-t-butyl carbonate was added to a solution in which 12 gof poly(p-hydroxystyrene) with Mw of 8,000 and 5 g of triethylamine weredissolved in 50 g of dioxane while stirring. The mixture was stirred for6 hours at room temperature. An aqueous solution of 3wt % oxalicacid wasthen added to neutralize triethylamine. The reaction solution wasdropped into a large quantity of distilled water to coagulate the resin.The coagulated resin was washed with distilled water several times. Theresin was then filtered and dried at 50° C. overnight under reducedpressure.

[0694] Mw and Mw/Mn of this resin were respectively 9,200 and 1.8. As aresult of ¹³C-NMR analysis, the resin was found to have a structure inwhich 30 mol % of hydrogen atoms of a phenolic hydroxyl group inpoly(p-hydroxystyrene) was replaced by t-butoxycarbonyl groups.

[0695] This resin is referred to as “acid-dissociable group-containingresin (B-6)”.

Synthesis Example 15

[0696] 24 g of poly(p-hydroxystyrene) with Mw of 12,000 was dissolved in100 g of dioxane. Nitrogen gas was bubbled through the mixture for 30minutes. After the addition of 3 g of ethyl vinyl ether, 3 g ofethyl-1-propenyl ether, and 1 g of pyridinium p-toluenesulfonate as acatalyst, the mixture was reacted for 12 hours at room temperature. Thereaction solution was dropped into a large quantity of 1 wt % ammoniumaqueous solution to coagulate the resin. The coagulated resin wasfiltered and dried overnight at 50° C. under reduced pressure.

[0697] Mw and Mw/Mn of this resin were respectively 15,000 and 1.6. As aresult of ¹³C-NMR analysis, the resin was found to have a structure inwhich 20 mol % of hydrogen atoms of a phenolic hydroxyl group inpoly(p-hydroxystyrene) was replaced by 1-ethoxyethyl groups, and 15 mol% by 1-ethoxy propyl groups.

[0698] This resin is referred to as “acid-dissociable group-containingresin (B-7)”.

Synthesis Example 16

[0699] 20 g of di-t-butyl carbonate was added to a solution in which 120g of poly(p-hydroxystyrene) with Mw of 12,000 and 15 g of triethylaminewere dissolved in 500 g of dioxane while stirring. The mixture wasstirred for 6hours at room temperature. An aqueous solution of 3 wt %oxalic acid was then added to neutralize triethylamine. The reactionsolution was dropped into a large quantity of distilled water tocoagulate the resin. The coagulated resin was washed with distilledwater several times. The resin was then filtered and dried at 50° C.overnight under reduced pressure.

[0700] Mw and Mw/Mn of this resin were respectively 8,900 and 2.8. As aresult of ¹³C-NMR analysis, the resin was found to have a structure inwhich 9 mol % of hydrogen atoms of a phenolic hydroxyl group inpoly(p-hydroxystyrene) was replaced by t-butoxycarbonyl groups.

[0701] This resin was dissolved in 100 g of dioxane and nitrogen gas wasbubbled through the solution for 30 minutes. After the addition of 2 gof ethyl vinyl ether, 2 g of ethyl-1-propenyl ether, and 1 g ofpyridinium p-toluenesulfonate as a catalyst, the mixture was reacted for12 hours at room temperature. The reaction solution was dropped into alarge quantity of 1 wt % ammonium aqueous solution to coagulate theresin. The coagulated resin was filtered and dried overnight at 50° C.under reduced pressure.

[0702] Mw and Mw/Mn of this resin were respectively 11,000 and 2.8. As aresult of ¹³C-NMR analysis, the resin was found to have a structure inwhich 14 mol % of hydrogen atoms of the phenolic hydroxyl group inpoly(p-hydroxystyrene) was replaced by 1-ethoxyethyl groups, 11 mol % by1-ethoxy propyl groups, and 9 mol% by t-butoxycarbonyl groups.

[0703] This resin is referred to as “acid-dissociable group-containingresin (B-8)”.

Synthesis Example 17

[0704] 25 g of a copolymer of p-hydroxystyrene and p-t-butoxystyrenewith a copolymerization of molar ratio of these monomers of 90:10 wasdissolved in 100 g of n-butyl acetate. Nitrogen gas was bubbled throughthe solution for 30 minutes. After the addition of 3.3 g of ethyl vinylether and 1 g of pyridinium p-toluenesulfonate as a catalyst, themixture was reacted at room temperature for 12hours. The reactionsolution was dropped into a large quantity of 1 wt % ammonium aqueoussolution to coagulate the resin. The coagulated resin was filtered anddried overnight at 50° C. under reduced pressure.

[0705] Mw and Mw/Mn of this resin were respectively 13,000 and 1.01. Asa result of ¹³C-NMR analysis, the resin was found to have a structure inwhich23mol % of hydrogen atoms of the phenolic hydroxyl group inpoly(p-hydroxystyrene) was replaced by ethoxyethyl groups, and 10 mol %by t-butyl groups.

[0706] This resin is referred to as “acid-dissociable group-containingresin (B-9)”.

Synthesis Example 18

[0707] 114 g of p-acetoxystyrene, 19 g of t-butyl acrylate, 32 g ofp-t-butoxystyrene, 6 g of azobisisobutyronitrile, and 1 g oft-dodecylmercaptan were dissolved in 230 g of propylene glycolmonomethyl ether. The mixture was polymerized at 70° C. for 16hours in anitrogen atmosphere. After the polymerization, the reaction solution wasadded dropwise to a large quantity of n-hexane to coagulate and purifythe resulting resin.

[0708] After the addition of 150 g of propylene glycol monomethyl etherto the resin, 300 g of methanol, 80 g of triethylamine, and 15 g ofdistilled water were added. The mixture was hydrolyzed for 8 hours whilerefluxing at the boiling point. After the reaction, the solvent andtriethylamine were evaporated under reduced pressure. The resultingresin was dissolved in acetone and added dropwise to a large quantity ofdistilled water to coagulate the resin. The resulting white powder wasfiltered and dried overnight at 50° C. under reduced pressure.

[0709] The resin was found to have Mw and Mw/Mn of 11,500 and 1.6respectively. The result of ¹³C-NMR analysis confirmed that the resinwas a copolymer of p-hydroxystyrene, t-butyl acrylate, andp-t-butoxystyrene at a copolymerization molar ratio of 65:15:20.

[0710] This resin is referred to as “acid-dissociable group-containingresin (B-10)”.

[0711] <Chemically amplified radiation-sensitive resin composition>

Examples 1-21 and Comparative Examples 1-2

[0712] Components shown in Table 1 were mixed to prepare homogeneoussolutions. The solutions were filtered through a membrane filter with apore diameter of 0.2 μm to prepare solution compositions.

[0713] The solution composition was spin-coated on a silicon wafersubstrate. PB was then performed under the conditions shown in Table 3to form resist coatings with a thickness of 0.5 μm from the compositionsof Examples 1-17, Examples 19-21, and Comparative Examples 1-2, and aresist coating with a thickness of 0.1 μm from the composition ofExample 18.

[0714] The resist coatings were exposed to radiations using a stepper“NSR2205 EX12B” (manufactured by Nikon Corp., numerical aperture: 0.55)in Examples 1-17 and Comparative Examples 1-2, an F₂ excimer laserexposure apparatus “XLS” (manufactured by Ultratech Corp., numericalaperture: 0.60) in Examples 18, and an electron beam lithography system“HL700” (manufactured by Hitachi, Ltd., acceleration voltage: 30 KeV) inwhich the acceleration voltage was remodeled to 50 KeV. PEB was theperformed under the conditions shown in Table 2.

[0715] The resist coatings were developed at 23° C. for 1 minute by apaddle method using a 2.38 wt % tetramethylammonium hydroxide aqueoussolution. The resist coatings were then washed with purified water anddried to form a resist pattern.

[0716] The results of the evaluation of each resist are shown in Table3.

[0717] Evaluation of resists was carried out as follows. Sensitivity

[0718] Sensitivity was evaluated based on an optimum exposure dose whichis a dose capable of forming a 1:1 line and space pattern (1L1S) with aline width of 0.22 μm, when a resist coating formed on a silicon wafersubstrate is exposed to light, immediately followed by PEB, development,washing with water, and drying.

[0719] Resolution

[0720] The minimum line and space (1L1S) dimension resolved by anoptimum does of irradiation was taken as the resolution.

[0721] Pattern profile

[0722] The cross-section of a line-and-space (1L1S) pattern with a linewidth of 0.22 μm was measured by a scanning electron microscope. Thepattern profile was evaluated according to the following standard,wherein La and Lb respectively indicate the line width at the top andbottom of the pattern cross-section.

Good: 0.9<La/Lb<1.1

Bad: 0.9≧La/Lb or La/Lb≧1.1

[0723] PED stability

[0724] A line and space pattern (1L1S) with a designed line width of0.26 μm was prepared in the same manner as the above resist patterns,except that PEB was performed after leaving the substrate after theexposure processing in a chamber in which the ammonia concentration wascontrolled to 5 ppb. The PED stability was evaluated according to thefollowing standard, wherein La indicates the line width at the top ofthe pattern.

Good: 0.85×0.26 μm<La<1.1×0.26 μm

Bad: La≦0.85×0.26 82 m or La≦1.1×0.26 μm

[0725] Storage stability

[0726] The sensitivity, resolution, and pattern profile were evaluatedusing the radiation-sensitive resin compositions stored at 23° C. for6months after preparation. The compositions showing the same evaluationresults as those as prepared, and exhibiting no development defects, andproducing no foreign matters after storage were deemed to have “Good”storage stability.

[0727] The acid generators (C), acid diffusion controllers, otheradditives, and solvents in Table 1 are as follows.

[0728] Acid generator (C)

[0729] C-1: bis(4-t-butylphenyl)iodonium nonafluoro-n-butanesulfonate

[0730] C-2: bis(4-t-butylphenyl)iodonium 10-camphorsulfonate

[0731] C-3: bis(4-t-butylphenyl)iodoniumtrifluoromethane sulfonate

[0732] C-4:N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyimide

[0733] C-5: bis(cyclohexanesulfonyl)diazomethane

[0734] C-6: triphenylsulfonium trifluoromethanesulfonate

[0735] C-7: N-(10-camphorsulfonyloxy)succinimide

[0736] Acid diffusion controller

[0737] D-1: tri-n-octylamine

[0738] D-2: triethanolamine

[0739] D-3: 2-phenylpyridine

[0740] D-4: N,N,N,N-tetrakis(2-hydroxypropyl)ethylenediamine

[0741] D-5: 2-phenylbenzimidazole

[0742] Other additives

[0743] E-1: 1-adamantane carboxylic acid

[0744] Solvent

[0745] S-1: ethyl lactate

[0746] S-2: ethyl 3-ethoxypropionate

[0747] S-3: propylene glycol monomethyl ether acetate

[0748] S-4: 2-heptanone TABLE 1 Carbazole Acid Acid derivative generatordiffusion Other (1) Resin (B) (C) controller additives Solvent Example 1A-1 (2) B-1 (100) C-4 (6) D-5 (0.2) — S-1 (500) Example 2 A-2 (2) B-1(100) C-4 (6) D-5 (0.2) — S-1 (500) Example 3 A-2 (2) B-2 (100) C-2 (2)D-4 (0.2) E-1 (0.1) S-1 (500) C-3 (2) Example 4 A-2 (2) B-3 (100) C-4(3) D-2 (0.2) — S-1 (500) C-7 (2) Example 5 A-2 (2) B-4 (100) C-4 (4)D-3 (0.2) — S-1 (500) Example 6 A-2 (2) B-5 (100) C-2 (1) D-1 (0.2) —S-1 (350) C-5 (5) S-3 (150) Example 7 A-2 (2) B-6 (100) C-5 (5) D-2(0.2) — S-1 (350) S-3 (150) Example 8 A-2 (2) B-7 (100) C-5 (5) D-2(0.2) — S-3 (500) Example 9 A-2 (2) B-8 (100) C-5 (4) D-2 (0.2) — S-1(350) C-2 (1) S-3 (150) Example 10 A-2 (2) B-9 (100) C-5 (5) D-5 (0.2) —S-1 (500) Example 11 A-2 (2) B-10 (100) C-5 (5) D-2 (0.2) — S-4 (500)Example 12 A-3 (2) B-1 (100) C-4 (4) D-5 (0.2) — S-1 (350) S-2 (150)Example 13 A-4 (2) B-1 (100) C-4 (4) D-5 (0.2) — S-1 (350) S-2 (150)Example 14 A-5 (2) B-1 (100) C-4 (4) D-5 (0.1) — S-1 (350) S-2 (150)Example 15 A-6 (2) B-1 (100) C-4 (4) D-5 (0.2) — S-1 (350) S-2 (150)Example 16 A-7 (2) B-1 (100) C-4 (4) D-5 (0.2) — S-1 (500) Example 17A-8 (2) B-1 (100) C-4 (4) D-5 (0.2) — S-1 (500) Example 18 A-2 (2) B-1(100) C-4 (4) D-5 (0.1) — S-1 (500) Example 19 A-2 (2) B-1 (100) C-4 (5)D-5 (0.1) — S-1 (500) Example 20 A-2 (2) B-2 (100) C-6 (3) D-5 (0.1) —S-1 (500) Example 21 A-2 (2) B-10 (100) C-5 (5) D-5 (0.1) — S-1 (500)Comparative — B-1 (100) C-1 (2) D-4 (0.2) E-1 (0.1) S-1 (500) Example 1C-3 (2) Comparative — B-1 (100) C-1 (6) D-4 (0.2) E-1 (0.1) S-1 (500)Example 2

[0749] TABLE 2 PB PEB Temp (° C.) Time (sec) Radiation Temp (° C.) Time(sec) Example 1 130 60 KrF excimer laser 130 60 Example 2 130 60 KrFexcimer laser 130 60 Example 3 130 60 KrF excimer laser 130 60 Example 4130 60 KrF excimer laser 130 60 Example 5 130 60 KrF excimer laser 13060 Example 6 100 60 KrF excimer laser 100 60 Example 7 90 60 KrF excimerlaser 100 60 Example 8 95 60 KrF excimer laser 100 60 Example 9 100 60KrF excimer laser 90 60 Example 10 90 60 KrF excimer laser 90 60 Example11 80 60 KrF excimer laser 90 60 Example 12 130 60 KrF excimer laser 12060 Example 13 120 60 KrF excimer laser 120 60 Example 14 110 60 KrFexcimer laser 130 60 Example 15 120 60 KrF excimer laser 130 60 Example16 130 60 KrF excimer laser 130 60 Example 17 130 60 KrF excimer laser130 60 Example 18 130 60 KrF excimer laser 130 60 Example 19 110 60Electronic beams 130 60 Example 20 110 60 Electronic beams 130 60Example 21 110 60 Electronic beams 130 60 Comparative 130 60 KrF excimerlaser 130 60 Example 1 Comparative 130 60 KrF excimer laser 130 60Example 2

[0750] TABLE 3 Resolution Storage Sensitivity (μm) Pattern profile PEDStability stability Example 1 100 J/m² 0.20 Good Good Good Example 2 120J/m² 0.21 Good Good Good Example 3 110 J/m² 0.19 Good Good Good Example4 130 J/m² 0.18 Good Good Good Example 5 90 J/m² 0.17 Good Good GoodExample 6 100 J/m² 0.19 Good Good Good Example 7 110 J/m² 0.20 Good GoodGood Example 8 100 J/m² 0.20 Good Good Good Example 9 100 J/m² 0.20 GoodGood Good Example 10 110 J/m² 0.20 Good Good Good Example 11 90 J/m²0.20 Good Good Good Example 12 80 J/m² 0.20 Good Good Good Example 13100 J/m² 0.20 Good Good Good Example 14 110 J/m² 0.18 Good Good GoodExample 15 120 J/m² 0.20 Good Good Good Example 16 90 J/m² 0.18 GoodGood Good Example 17 100 J/m² 0.19 Good Good Good Example 18 50 J/m²0.17 Good Good Good Example 19 2 × 10⁻² C/m² 0.17 Good Good Good Example20 3 × 10⁻² C/m² 0.17 Good Good Good Example 21 3 × 10⁻² C/m² 0.18 GoodGood Good Comparative 340 J/m² 0.22 Good Good Good Example 1 Comparative100 J/m² 0.22 Bad Good Good Example 2

[0751] The radiation-sensitive resin composition (1) of the presentinvention is non-sublimable and very useful as a sensitizing componenetof a chemically amplified resist which is sensitive to active rays suchas deep ultraviolet rays represented, for example, by a KrF excimerlaser (wavelength 248 nm), ArF excimer laser (wavelength: 193 nm), andF₂ excimer laser (wavelength: 157 nm). The chemically amplifiedradiation-sensitive resin composition containing the carbazolederivative (1) of the present invention can be used as a chemicallyamplified resist, which particularly exhibits high sensitivity withoutlosing basic properties as a resist such as resolution and patternprofile. The composition also exhibits superior environmental resistancesuch as PED stability and excellent storage stability.

[0752] Obviously, numerous modifications and variations of the presentinvention are possible in light of the above teachings. It is thereforeto be understood that, within the scope of the appended claims, theinvention may be practiced otherwise than as specifically describedherein.

What is claimed is:
 1. A carbazole derivative of the following formula(1),

wherein R¹ and R² individually represent a hydrogen atom or a monovalentorganic group, or R¹ and R² form, together with the carbon atom to whichR¹ and R² bond, a divalent organic group having a 3-8 member carbocyclicstructure or a 3-8 member heterocyclic structure, and R³ represents ahydrogen atom or a monovalent organic group.
 2. The carbazole derivativeaccording to claim 1, wherein the monovalent organic group representedby R¹ and R ² in the formula (1) is a linear, branched, or cyclic alkylgroup having 1-12 carbon atoms, aromatic hydrocarbon group having 6-20carbon atoms, oxygen-containing organic group, nitrogen-containingorganic group.
 3. The carbazole derivative according to claim 1, whereinthe monovalent organic group represented by R¹ and R² in the formula (1)is a hydrogen atom, methyl group, ethyl group, n-propyl group, i-propylgroup, n-butyl group, 2-methylpropyl group, 1-methylpropyl group,t-butyl group, phenyl group, or benzyl group, or a divalent organicgroup having an alicyclic ring formed by R¹, R², and the carbon atom towhich R¹ and R² bond, which is derived from cyclohexane.
 4. Thecarbazole derivative according to claim 1, wherein the monovalentorganic group represented by R³ in the formula (1) is a linear,branched, or cyclic alkyl group having 1-12 carbon atoms, aromatichydrocarbon group having 6-20 carbon atoms, oxygen-containing organicgroup, nitrogen-containing organic group, or acid-dissociable organicgroup.
 5. The carbazole derivative according to claim 1, wherein themonovalent organic group represented by R³ in the formula (1) isahydrogen atom, methyl group, ethyl group, n-propyl group, n-butylgroup, 2-methylpropyl group, or phenyl group, or an acid-dissociableorganic groups selected from the group consisting of an i-propyl group,1-methylpropyl group, t-butyl group, cyclohexyl group, benzyl group,t-butoxycarbonylmethyl group, 1-methoxyethyl group, 1-ethoxyethyl group,trimethylsilyl group, t-butoxycarbonyl group, tetrahydrofuranyl group,tetrahydropyranyl group, tetrahydrothiofuranyl group, andtetrahydrothiopyranyl group.
 6. The carbazole derivative according toclaim 1, wherein R³ in the formula (1) is an i-propyl group, t-butylgroup, cyclohexyl group, or benzyl group.
 7. The carbazole derivativeaccording to claim 1, wherein R¹ and R² in the formula (1) are hydrogenatoms.
 8. The carbazole derivative according to claim 1, wherein R³ inthe formula (1) is an acid-dissociable organic group.
 9. A chemicallyamplified radiation-sensitive resin composition comprising the carbazolederivative of claim
 1. 10. A positive tone radiation-sensitive resincomposition comprising (A) the carbazole derivative of claim 1, (B) anacid-dissociable group-containing resin which is insoluble or scarcelysoluble in alkali, but becomes alkali soluble when the acid-dissociablegroup dissociates, and (C) a photoacid generator.
 11. The chemicallyamplified radiation-sensitive resin composition according to claim 10,comprising the carbazole derivative (A) in an amount of 0.1-40 parts byweight for 100 parts by weight of the acid-dissociable group-containingresin (B).
 12. The chemically amplified radiation-sensitive resincomposition according to claim 10, wherein the acid-dissociablegroup-containing resin (B) is a resin obtainable from apoly(p-hydroxystyrene), a copolymer of p-hydroxystyrene andp-hydroxy-α-methylstyrene, a copolymer of p-hydroxy styrene and styrene,or a copolymer of p-hydroxy styrene and/or p-hydroxy-α-methylstyrene and(meth) acrylic acid by replacing a part or all of the hydrogen atoms inthe phenolic hydroxyl groups or the hydrogen atoms in the carboxylicgroups with an acid-dissociable group.
 13. The chemically amplifiedradiation-sensitive resin composition according to claim 10, wherein theacid-dissociable group is a substituted methyl group, 1-substitutedethyl group, 1-branched alkyl group, silyl group, germyl group,alkoxycarbonyl group, acyl group, or cyclic acid-decomposable group. 14.The radiation-sensitive resin composition according to claim 10, whereinthe amount of the acid-dissociable groups introduced into theacid-dissociable group-containing resin (B) is 15-100%.
 15. Theradiation-sensitive resin composition according to claim 10, wherein thephotoacid generator (C) is at least one compound selected from the groupconsisting of onium salt compounds, sulfone compounds, sulfonatecompounds, sulfonimide compounds, disulfonyldiazomethane compounds,disulfonylmethane compounds, oximesulfonate compounds, and hydrazinesulfonate compounds.
 16. The chemically amplified radiation-sensitiveresin composition according to claim 10, comprising the photoacidgenerator (C) in an amount of 0.1-20 parts by weight for 100 parts byweight of the acid-dissociable group-containing resin (B).
 17. Thechemically amplified radiation-sensitive resin composition according toclaim 10, further comprising an acid diffusion controller.
 18. Thechemically amplified radiation-sensitive resin composition according toclaim 17, wherein the acid diffusion controller is a nitrogen-containingorganic compound.